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  • Articles  (1,977)
  • American Institute of Physics (AIP)  (1,881)
  • Blackwell Publishing Ltd
  • 1985-1989  (1,977)
  • 1987  (1,977)
  • Chemistry and Pharmacology  (1,906)
  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (71)
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  • Articles  (1,977)
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  • 1985-1989  (1,977)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5141-5148 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A pure rotational spectrum of SnH4 has been studied in the ν4 state by infared–microwave double resonance with a tunable diode laser. Twenty-seven double resonance signals have been observed for the 11 JJ–JJ type rotational transitions of the 5 Sn isotopic species. An infrared spectrum of the Coriolis-coupled ν2 and ν4 bands has been measured using a diode laser with Doppler-limited resolution. The ground-state scalar constants, B0, D0, and H0, have been determined by taking combination differences in the "forbidden'' ν2 band, which borrows intensity through a strong Coriolis interaction. The observed microwave and infrared data have been analyzed simultaneously by including the Coriolis interaction explicitly. More than 20 molecular constants have been determined accurately for the ν2/ν4 dyad of seven major isotopic species.
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  • 2
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5149-5155 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The lowest Π bending state in Ar–HCl has been more completely characterized through the use of far infrared laser/microwave double resonance spectroscopy. This extended analysis includes a partial reassignment of the far infrared spectra of Ar–H35Cl previously reported by Ray et al. and by Marshall et al., as well as an analysis of the ArH37 Cl spectra. Improved molecular constants have been determined. The value of the rotational constant is now in good agreement with that calculated by Hutson from the M5 double minimum potential surface. Along with the recently reported spectrum of the Σ bending vibration, this extended analysis provides strong evidence for the existence of two minima character in the intermolecular potential surface of Ar–HCl.
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  • 3
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5156-5160 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The first high-resolution measurement of a van der Waals stretching vibration is reported. The ν3 fundamental stretching vibration in Ar–HCl has been measured by intracavity far infrared laser/microwave double resonance spectroscopy of a supersonic free jet. Coupling between the stretching state and the nearby bending states gives the spectrum an intensity which is greater than predicted. The molecular constants for the stretching state are in close agreement with calculations by Hutson for the M5 potential surface.
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  • 4
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5186-5194 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: With two cw single mode dye lasers selective two-step excitation of Rydberg levels of the Li2 molecule is achieved which is detected by optical double resonance polarization spectroscopy. The Doppler-free DR signals allow accurate measurements of rotational perturbations which cause level shifts and intensity anomalies due to interference phenomena. The experimental results are discussed and molecular constants for the deperturbed Rydberg states are given, which, together with the coupling matrix elements allow the accurate reproduction of the measured spectra.
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  • 5
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5176-5185 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Polarized Raman spectra of Langmuir–Blodgett multilayers of barium stearate have been studied in the 2800–3000 cm−1 region (C–H stretching vibrations). The samples have been excited by evanescent waves produced by the plasmon illumination method. Only TM excitation can be used for very thin films. Therefore the polarized Raman spectra are complex, but, due to the smallness of some nondiagonal terms of the Raman tensor, these spectra are similar to the pure polarized spectra given by the TE excitation. When the film thickness decreases from 122.5 to 22.5 nm, the spectra are only slightly modified. The study of the ν(C–C) lines in the 1000–1200 cm−1 region have shown that the chains are still all-trans plane. With ultrathin films (〈20 nm) changes are observed in the shape and in the polarization of the 2800–3000 cm−1 band. The first modification (appearance and disappearance of shoulders or peaks) is attributed to conformational change of the acyl chains. The second modification (unpolarization) is related to the deformation of the monolayer deposited on the prism surface which is rough relative to the molecular dimensions. It seems that only the first three layers are concerned by this deformation.
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  • 6
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5161-5175 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the first optical dephasing study of an inorganic impurity system possessing sharp, low frequency mode structure in its ground and excited state spectra. The total dephasing times T2 and population relaxation times T1 for the 1T2g and 1Eg d9s excited states of NaF:Cu+ are determined at a series of temperatures between 1.8 and 296 K. The T2 values are determined by extracting the Lorentzian components from one- and two-photon excitation line shapes. The T1 values caused by nonradiative decay rates are obtained by detecting very low quantum yield emission from the fast-relaxing excited states and applying the formula tnr=Qtr, where t's are radiative and nonradiative lifetimes and Q is the quantum yield. T1(1T2g)=4.6 ps and T1(1Eg )=2.0 ps at 8 K. Significantly, these are very similar to the T1 values calculated from lowest temperature Lorentzian linewidths by the relationship 1/T2=1/T′2 +1/(2T1). The T1 values stay approximately constant over the temperature range 1.8–45 K, while the linewidths rapidly increase indicating that pure dephasing dominates. Using ground and excited state information on the low frequency modes, we test optical Redfield theory and the nonperturbative harmonic theory for pure dephasing by pseudolocal phonons against data for this system which displays strongly anhamonic progressions. The nonperturbative theory fits the line broadening data to higher temperatures than optical Redfield theory for the least anharmonic excited state potential, 1T2g. Both theories underpredict the broadening with temperature of the extremely anharmonic 1Eg state. A simple anharmonic theory including scattering to overtone levels also fails to predict the observed linewidth temperature behavior, although it is demonstrated these processes should be occurring.
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  • 7
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5195-5201 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The proximity of the L2 (2p1/2) ionization potential in germanium compounds to the MgKα radiation energy introduces threshold ionization effects in the Ge LMM Auger spectra derived from this level. The spectra of GeH4, Ge(CH3)4, Ge(C2H5)4, GeF4, and GeCl4 excited with MgKα radiation are compared with those excited with AlKα radiation and post-collision interaction (PCI) and spectator satellite effects induced are analyzed. Comparison of L2,3M2,3M4,5 and L2,3M4,5M4,5 spectra reveal a final state dependence of the satellite shifts.
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  • 8
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5202-5208 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectrally resolved infrared fluorescence near 10 μm from vibrationally excited O3(ν3) has been observed in a cryogenic reactor facility at low pressure. The excited O3(v) is formed principally by three-body recombination of O and O2 in flowing, microwave-discharged O2/Ar mixtures at 1 Torr and 80 K. The spectral resolution is sufficient to permit identification and assignment of band centers for up to five quanta of stretching excitation. The observed transition frequencies are consistent with those predicted from a Darling–Dennison perturbation treatment. The spectra, which sample the recombination/deactivation sequence in its early to middle stages, indicate surprisingly little intermode coupling, being predominantly ν3 in character. There is also evidence of O3(v) excitation by near-resonant V–V coupling between O3 and O2(v=2). The spectroscopic analysis of the data is described, and considerations for scaling the spontaneous transition probabilities with vibrational level are discussed.
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  • 9
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5222-5228 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The problem of the diffusion controlled recombination of ions for the case where initially two or more pairs of oppositely charged ions are found in each other's Coulomb field, as occurs in the track of a high-energy electron in a nonpolar liquid, is treated by means of computer simulation. Results are presented on the probability of survival as a function of time for ion pairs in clusters containing up to four ion pairs initially. The effect of an external electric field on the probability of escape from recombination is investigated. The multipair results are compared with the calculations based on the single-pair theory. The consequences of the consideration of multipair effects in addition to the single ion-pair contribution in the nonhomogeneous kinetics of the track of high-energy electron in nonpolar liquids are discussed briefly.
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  • 10
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5209-5221 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectrally resolved infrared chemiluminescence from vibrationally excited ozone, O3(v), has been used to study the reaction kinetics of O3(v) in discharged O2/Ar mixtures at ∼1 Torr and 80–150 K. Dependences of the excited state number densities on temperature and O2 mole fraction indicate O3(v) is formed primarily by three-body recombination of O with O2 and is destroyed by rapid chemical reaction with O. Several secondary excitation reactions involving vibrationally and electronically excited O2 are also indicated. The data are treated with a detailed steady-state analysis of the discharge kinetics, to extract estimates for rate coefficients of the key elementary reactions. The effective "quasinascent'' state distribution in recombination is also inferred; this distribution shows selective recombination into the asymmetric stretching mode, but an apparently statistical (i.e., collisionally scrambled) behavior among the vibrational states within that mode. The results are discussed in terms of the detailed dynamics of three-body recombination.
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  • 11
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5238-5241 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Clusters of Ne atoms produced by adiabatic nozzle expansion have been studied with a high resolution double focusing sector field mass spectrometer. Analysis of the isotopic composition of these clusters (up to n=22) showed instead of the expected statistical distribution a pronounced shift to the heavier neon isotope 22Ne. The shift was found to correspond to an increase of the isotope ratio of 22Ne from 8.7% in the monomer to ∼12.5% in the clusters with n〉4 (enrichment factor of ∼1.5.)
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  • 12
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5229-5237 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate the rotational energy transfer of H35Cl (v=1) in collisions with thermal HCl at 298 K. Rotationally state-selective excitation of v=1 over J=1–6 is achieved by stimulated Raman pumping, and the rotational relaxation from the initially pumped level is monitored via 2+1 resonantly enhanced multiphoton ionization (REMPI) through the E 1Σ+–X 1Σ+0–1 band. The ions are detected in a time-of-flight mass spectrometer in order to ensure that only relaxation of H35Cl is observed. We present empirical correction factors for determining relative rotational populations from the REMPI spectral line intensities and extract the rate constants for rotational energy transfer from the time-dependent populations using numerical techniques. The excellent sensitivity of the REMPI technique makes it possible to monitor the relaxation on very short collisional time scales (〈0.1 hard sphere collision) and thereby enables us to determine the rate constants for both single quantum and multiquanta rotational transitions directly, without the use of a simplifying model for the matrix of rate constants. The measured rate constants illustrate the importance of multiquanta transitions for HCl; such transitions account for ∼30% of the total population loss from a given rotational level. We compare our rate constants to those obtained in previous measurements on HCl (v=1) and HF (v=2). We find that the rate constants are not adequately described by models based solely on the rotational energy defect of the vibrationally excited molecule.
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  • 13
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5251-5255 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper reports the results of two related experiments: (A) The state-to-state rotational transition probabilities of N2(a 1Πg) in collisions with rare gas atoms (Ar or He) were measured by the technique of two-step multiphoton ionization. Results show that the selection rule antisymmetric–symmetric is obeyed. The transition probability drops rapidly with increasing ||ΔJ||. A propensity rule related to the Π+ or Π− symmetry conservation of the electronic wave function during the collision induced rotational transition holds. (B) The cross section for the rovibronic energy transfer between N2(1Πg) and N2(X 1Σ+g) is found to be ∼28 A(ring)2. N2(a 1Πg) product populations show a Boltzmann-like distribution with a rotational temperature suggesting an equipartition of the available energy among the rotational and translational degrees of freedom of the products. A mechanism invoking an intermediate collision complex along with intermolecular electron exchange may explain the results.
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  • 14
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    The Journal of Chemical Physics 87 (1987), S. 5266-5271 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Absolute integral cross sections for collisions of CH4 with O2 molecules and of O2 molecules and O(3Pj) atoms with CH4 are measured as a function of velocity at thermal energies in a molecular beam apparatus. For the O2–CH4 interaction the glory structure observed allows an analysis in terms of an isotropic potential model and meaningful potential parameter values are obtained. For the O(3Pj)–CH4 interaction the anisotropy due to the O(3Pj) atoms causes a partial quenching of the glory amplitude. Nevertheless a realistic isotropic potential can be extracted from the glory extrema position. The present potential parameters for the O2–CH4 and the O–CH4 interactions can be used to predict realistic parameters for more complicated interactions involving O2 molecules and O atoms with other species of interest also in combustion.
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  • 15
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5242-5250 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dissociation dynamics of energy selected n-propanol ions have been investigated by photoelectron photoion coincidence (PEPICO) and laser photodissociation. In spite of the low activation energy, the dissociation rates for the loss of H2O were found to be slow (〈106 s−1) near the dissociation limit, but they increase rapidly with ion internal energy. The photodissociation experiment indicates that the n-propanol ion structure is maintained up to the dissociation limit. However, the reaction rate and the kinetic energy release show that H2O loss proceeds via an isomerized C3H8O+ structure. Ab initio calculations suggest that the isomerized structure is the ion–dipole complex formed by the cyclopropane ion and water. The dissociation rate is calculated with the statistical theory (RRKM/QET) by using vibrational frequencies determined from the ab initio calculation. Although the ion–dipole complex potential well is deeper than that of propanol, it does not account for the slow dissociation rate. The discrepancy of more than four orders of magnitude is attributed to the extremely anharmonic interaction potential associated with the ion–dipole forces.
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  • 16
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    The Journal of Chemical Physics 87 (1987), S. 5256-5265 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Inelastic and charge transfer scattering of protons by water molecules at collision energies of 27.0 and 46.0 eV have been investigated in a high-resolution crossed beam experiment up to the rainbow scattering angles. Excitation of the stretching (symmetric or asymmetric) and bending mode vibrations within the electronic ground state, X 1A1, of H2O was observed in the proton energy-loss spectra. In the case of charge transfer, formation of H2O+ in the X˜ 2B1 and A˜ 2A1 electronic states was identified in the corresponding H-atom spectra; the vibrational states within the X˜ and A˜ bands were for the most part resolved and, at small angles (θ≤2°), they were found to be nearly the same as in photoionization (symmetric stretch and bending mode excitation within the X˜ state and pure bending mode excitation within the A˜ state). The vibronic transition probabilities deviate, however, considerably from the corresponding Franck–Condon factors in favor of the enhancement of the quasiresonant states. For both the inelastic and charge transfer scattering, state-selected quantities characteristic of the detailed collision dynamics have been derived. In addition, rotational excitation superimposed on the vibrational transitions could be estimated and for both processes it was found to be of the order of 50–100 meV.
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  • 17
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    The Journal of Chemical Physics 87 (1987), S. 5272-5279 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The quasidissipative intramolecular dynamics of experimentally prepared nonstationary states in large, isolated polyatomic molecules are examined using an adaptation of the adiabatically reduced coupled equations approach [J. Chem. Phys. 84, 2254 (1986)]. Under appropriate conditions, the present method predicts an exponential decay of the initial state probability which has a "generalized'' Golden Rule-like decay rate constant. The present dynamical approach is complementary to approximate resolvent operator techniques commonly employed in radiationless transitions theory.
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  • 18
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    The Journal of Chemical Physics 87 (1987), S. 5302-5311 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We propose an extension of the semiclassical Gaussian wave packet dynamics to eliminate the three main restrictions of this method. The first restriction is that the wave packet is forced to remain Gaussian. This is correct only for quadratic, linear, or constant potentials. The second restriction is that the method is, in general, not able to treat most classically forbidden processes. The third restriction is that the norm is conserved only for Gaussian wave packets. For a superposition of Gaussians this is no longer true. We can eliminate these restrictions by an extension of the method into complex phase space, keeping time real.
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  • 19
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    The Journal of Chemical Physics 87 (1987), S. 5294-5301 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rate constants for the vibrational relaxation of 12C16O(v=1) and 13C18O(v=1) by 4He and 3He over an ab initio potential surface have been calculated with a vibrational close-coupling, rotational infinite order sudden (VCC-IOS) technique. Improved experimental measurements of the relaxation of 12C16O(v=1) by 4He and new measurements of the deactivation of 13C18O(v=1) by 4He and 3He all over the temperature range 300–80 K have been carried out with a laser fluorescence method. These rate constants and existing ones for the deactivation of 12C16O by 4He over the temperature range 2300–580 K and by 3He over the temperature range 300–80 K are compared with the theoretical rate constants. The rate constants vary by over six orders of magnitude but the calculations reproduce the experimental values well. These results give evidence for the accuracy of the potential energy surface and the (IOS) technique.
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  • 20
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    The Journal of Chemical Physics 87 (1987), S. 5280-5293 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a study of the dehydrohalogenation reactions of Li+ with isopropyl chloride (IPC), n-propyl chloride (NPC), and isopropyl bromide (IPB) over the collision energy range from 0.6 to 1.7 eV. Full differential cross sections at collision energies up to 1.2 eV show increasing asymmetry in the angular distributions as a function of initial collision energy and suggest that the reactions take place on a time scale of 0.2 ps. The observation of Li+ nonreactively ejected from the initial encounter complex formed by approaching reactants is consistent with a double minimum reaction coordinate and a comparison of the nonreactive flux with the flux for elimination products allows an estimate of the heights of intermediate isomerization barriers separating the wells on the potential surface. The barrier heights are in the order IPC〈IPB〈NPC, consistent with a transition state at the isomerization barrier in which a significant charge has developed on the carbon attached to the halogen. The kinetic energy distributions for Li+(HX) and Li+(C3H6) products and nonreactively scattered Li+ are in reasonable agreement with phase space theory calculations which include all product vibrational modes. The energy dependence of the Li+(HX)/Li+(C3H6) branching ratio can be accounted for quantitatively by statistical calculations which include the increasing importance of dissociation of the products with increasing collision energy. The discrepancy between the statistical recoil energy distributions and apparent complex lifetimes several orders of magnitude shorter than the predictions of RRKM theory can be understood in terms of incomplete transfer of energy from the incident Li+ to the internal degrees of freedom of the initial encounter complex, resulting in a density of complex states much lower than statistical.
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  • 21
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    The Journal of Chemical Physics 87 (1987), S. 5312-5316 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A recently developed classical model for the simulation of overtone dynamics in C6H6 and C6D6, is used to evaluate estimates for the decay times of CH and CD overtones in all deuterated benzenes for which experimental linewidths have been measured. The calculated and inferred decay times are compared for C6H6, C6H5D, p-C6H2D4, C6HD5, and C6D6. Reasonable quantitative agreement between theory and experiment is reported and marked qualitative trends are reproduced.
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  • 22
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    The Journal of Chemical Physics 87 (1987), S. 5325-5328 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A method has been developed to allow calculation of the electronic dipole and transition moments of diatomic molecules directly from the relativistic CI wave function. In this way, the effect of spin–orbit coupling on these quantities may be rigorously ascertained. The electric dipole moment of the ground state of HI is calculated and compared to experimental data and nonrelativistic all-electron results. Transition moments between the ground state and two low-lying electronic states of HI are also calculated in the relativistic CI formalism to illustrate how the effect of spin–orbit interaction on transition moments can be studied.
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  • 23
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    The Journal of Chemical Physics 87 (1987), S. 5317-5324 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper presents the detailed results of a quasiclassical trajectory surface hopping study of reaction of highly vibrationally excited H+2 with ground state H2 (and isotopic counterparts H+2 +D2, D+2 +H2, and D+2 +D2 ), with particular emphasis on the formation and decay of metastable H+3 products. A diatomics-in-molecules surface is used which has been successful in previous studies of H+2 (v) + H2 at low v. In the present study, we consider v=0–17, and find that metastable H+3 's are a major product for v≥13. Some of these metastables decay rapidly, showing exponential lifetime distributions with 2–7 ps lifetimes depending on v and on isotope. The remaining H+3 's have much longer lifetimes, and a number of methods are used to determine the origin of their stability. In no cases are any of these molecules found to be quasiperiodic, but a Fourier spectral analysis reveals some decoupling of H+ –H2 orbital motion from H2 rotational motion, and we find that many molecules have long lifetimes even though they have energies which are above any rigorous centrifugal barrier. The relation of these results to recent infrared absorption measurements on highly excited H+3 's is discussed.
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  • 24
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    The Journal of Chemical Physics 87 (1987), S. 5329-5332 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A study of the 1 B1 and 3 B1 states of CH2 has been carried out, with the aim of evaluating the singlet–triplet differences in the total energy and its components. These were examined in connection with the interpretation of Hund's multiplicity rule. Although vertical results near equilibrium tend to vindicate the new explanation of Hund's rule, the effect of the molecular virial theorem must be considered at large separations. Also, for adiabatic comparisons, the effect of bond lengths on the energy components must be considered. Correlation energy was found to have a significant effect on vertical energy component differences at certain geometries.
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  • 25
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    The Journal of Chemical Physics 87 (1987), S. 5333-5337 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The valence ionization spectrum and the electron affinity are calculated for the two nearly degenerate 1 A1 states of S3, the open (C2v) and the closed (D3h) form. Electron correlation and relaxation effects are included via the Green's function method. The theoretical ionization spectra are rather different. The D3h isomer has the lower ionization energy and the first band (at about 8.9 eV) is separated from the next band system by about 3.5 eV. The spectrum of the C2v isomer should at the ionization threshold with an ionization energy of about 9.8 eV consist of three nearly degenerate bands. The experimental value is 9.68 eV. Satellite lines are calculated to be very dominant in the case of the open form. Only the open form has an electron affinity which is calculated to be 2.07 eV (vertical value) and the adiabatic value is estimated to be 2.34 eV. This is to be compared with the experimental (adiabatic) value of 2.093 eV. The electron affinity of the other form is close to zero.
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  • 26
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    The Journal of Chemical Physics 87 (1987), S. 5338-5345 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ground state potential energy curves of alkali (LiH to CsH) and alkaline–earth monohydrides (BeH to BaH) have been calculated. A pseudopotential formalism including a core-polarization potential has been used. For the valence correlation energy, two different methods, the local spin-density functional and the configuration interaction with single and double excitations, have been employed. Dissociation energies, bond lengths, vibrational frequencies, anharmonicity constants, and dipole moments are reported. The agreement with experimental values, where available, is very good. A discussion and a comparison with other theoretical values, at different levels of approximation, are also included.
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  • 27
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    The Journal of Chemical Physics 87 (1987), S. 5346-5360 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theoretical analysis has been made of the van der Waals vibration–rotation–electron spin states of the O2–O2 dimer in its 3Σ−g –3Σ−g electronic ground state. This analysis is based on a Hamiltonian that includes a spin-dependent O2–O2 interaction potential and it involves also the permutation–inversion symmetry of the system. We have constructed some hindered internal rotor models for the vibrational states of the O2–O2 dimer which correspond with different equilibrium geometries, and for each of these models we have numerically calculated the spin-rotation fine structure. This fine structure appears to be determined not only by the Heisenberg exchange interaction between the O2 monomer triplet states, but also by intramolecular spin–orbit and spin–spin coupling and, to a smaller extent, by the intermolecular spin–spin (magnetic dipole) interaction and by the Coriolis terms in the kinetic energy. The resulting fine-structure spectrum is very complex, and very sensitive to the geometry of the O2–O2 dimer, to the nature of its internal motions and to the various magnetic couplings. This implies that detailed measurements of this spectrum, which can be interpreted with the help of the theory presented here, will yield interesting information on the properties of the O2–O2 dimer and, at the same time, verify our assumptions on the magnetic interactions between O2 molecules which have important consequences for the properties of solid oxygen.
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  • 28
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    The Journal of Chemical Physics 87 (1987), S. 5361-5373 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The theory for the analytic evaluation of energy gradients for coupled cluster (CC) wave functions is presented. In particular, explicit expressions for the analytic energy gradient of the CC singles and doubles (CCSD) wave function for a closed-shell restricted Hartree–Fock reference determinant are presented and shown to scale as N6 where N is the one-electron number of atomic basis functions for the molecular system. Thus analytic CCSD gradients are found to be of the same magnitude in computational cost as is the evaluation of analytic gradients for the configuration interaction singles and doubles (CISD) wave function. Applications of this method are presented for the water molecule and the formaldehyde molecule using a double-ζ plus polarization (DZ+P) basis set. The CCSD equilibrium geometries, dipole moments, and, via finite differences of gradients, CCSD harmonic vibrational frequencies and infrared intensities are reported. For H2O these results are compared to analogous CISD, CISDT, CISDTQ, and experimental results, and it is found that the CCSD predictions are most comparable to those of CISDTQ for this particular system. For the case of H2CO, the CCSD results are compared to CISD and experimental predictions. In general, the CCSD results and timings are encouraging.
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  • 29
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    The Journal of Chemical Physics 87 (1987), S. 5374-5385 
    ISSN: 1089-7690
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    Topics: Physics , Chemistry and Pharmacology
    Notes: In chemical applications of the Jahn–Teller effect, the shape of the adiabatic potential near the instability point is of primary importance. The present article examines this shape, both in the usual representation in the space of the nuclear configurations and in the less current projective representation in the space of the electronic functions. The general structural aspects of these representations are viewed as the results of a symmetry breaking process, starting at the continuous invariance group of the degenerate coupling limit, and ending with the finite point group of the representation space. The various vibronic coupling mechanisms involved in this process are characterized by irreducible tensor functions of the full orthogonal groups. The leading tensorial rank of the unequal linear coupling mechanism is shown to be four, while the bilinear coupling mechanism also involves an irreducible component of the sixth rank. This tensorial analysis provides a grouptheoretical foundation for the recently formulated epikernel principle, which predicts the location of extremal points on a Jahn–Teller surface.
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  • 30
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    The Journal of Chemical Physics 87 (1987), S. 5386-5392 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The algebraic resonance quantization (ARQ) method has previously been investigated for coupled Morse oscillators with moderate coupling and a substantial degree of classical chaos. This method is investigated here for strong coupling with the transition to global chaos and a Wigner distribution of level spacings in the quantum spectrum. A sparse matrix multiresonance approximation (SMRA) is found to give good results even when there is global chaos. A truncated basis set approximation (TMRA) is successful for moderate coupling but breaks down for strong coupling. Implications of these results for calculation of rotation–vibration levels of polyatomics in the regime of global chaos are discussed. Prospects for nonlinear least-squares fitting of experimental spectra in the regime of global chaos are also discussed.
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  • 31
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    The Journal of Chemical Physics 87 (1987), S. 5403-5414 
    ISSN: 1089-7690
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Formal solutions to the exact BGY equations of the single occupancy model of classical anharmonic solids have been developed and approximate solutions have also been constructed on the basis of the "consistent'' closure relation. The partition function of the system is determined by the normalization condition of the singlet function ρ1 and the total distribution function ρN through the use of the linked hierarchical relationship between distribution functions. It is explicitly proved that the free energy expression, the virial pressure, and the energy equation are all consistent at all orders of truncation approximation. A new method to calculate solid-phase entropy in Monte Carlo experiments is also proposed based on the free energy we developed and applied to inverse 12th-power systems to give a numerical example.
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  • 32
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    The Journal of Chemical Physics 87 (1987), S. 5393-5402 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We report a theoretical study of the barrierless electronic relaxation in solution. The existing theoretical models are divided into two classes: (A) Instantaneous death models where the excited state decays with unit probability as soon as it attains certain critical conformations, and (B) finite decay models, where the decay from the critical geometries occur at a finite rate (=k0). All the models belonging to class (A) predict inverse friction (ζ) dependence of the nonradiative decay rate if the radiative relaxation is neglected. These models predict that the long time decay rate is independent of the excitation wavelength although the average rate (so the quantum yield) show a strong dependence. The relaxation behavior of models (B) is controlled by the dimensionless parameter k˜0(=k0ζ/ω2μ, where ω is the frequency of the excited state surface and μ is the effective mass of the reactive motion). A fractional friction dependence of the long time rate is obtained at low to intermediate values of k˜0, but an inverse friction dependence is predicted for large values of this parameter. The fractional dependence of the average rate on viscosity is found to depend critically on the wavelength of the exciting light. A small negative activation energy is found at small values of k˜0. A delta-function sink (DFS) is introduced to simplify numerical calculations. This DFS model retains the essential features of the more realistic Gaussian sink model. The DFS model is studied both analytically and numerically. We find that the asymmetry in the position of the sink function, with respect to the minimum of the excited state potential surface, can play an important (hidden) role in the relaxation process. Especially, it can give rise to a significant temperature coefficient of the rate and can lead to an erroneous conclusion on the "molecular'' activation energy. Finally, systematics of fitting the experimental data to the present theories are discussed.
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    The Journal of Chemical Physics 87 (1987), S. 5415-5418 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper reports analytical approximations to the level-spacing distributions for two types of eigenspectra: a Gaussian orthogonal ensemble (GOE) eigenspectrum, a fraction of whose levels are omitted, and the superposition of a fractional GOE distribution with levels from a random sequence. The combined distribution would be expected when a spectrum with a GOE spacing distribution is observed, but with insufficient dynamic range to observe all the lines, and with the possibility of contamination from other sequences or from noise identified as spectral lines. Berry recently demonstrated that GOE type spacing statistics are expected in the semiclassical limit of a classically chaotic Hamiltonian. Therefore, the present formula may prove useful in testing for quantum signatures of classical chaos in quantum molecular spectra.
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    The Journal of Chemical Physics 87 (1987), S. 5419-5424 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Valence bond, SCF, and MP4SDQ calculations are reported for three low lying states of the HeO+ molecular ion; 4Σ(4S), 2Π(2D), and 2Π(2P). Together with the two-temperature theory of ion transport, these interaction potentials have been used to calculate the drift velocity and reduced mobility of O+ in helium as a function of the electric field to gas number density ratio. The calculated HeO+(4Σ) interaction potentials adequately describe the mobility of ground state O+ in helium, however, the O+(2D) mobility calculated using the 2Π(2D) interaction potential does not match the experimental mobility measurements for the metastable O+* ion which have been reported as the O+(2D) state. An interaction potential is reported for HeO+[2Π(2P)] which will reproduce the experimental mobility of O+*.
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    The Journal of Chemical Physics 87 (1987), S. 5425-5436 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We describe a general perturbation method that can be used to solve the equilibrium and critical-point conditions for model systems described by an analytic Helmholtz free energy. The general technique is developed within the framework of continuous or polydisperse systems; it may be applied to systems with discrete components, as well as to systems described by a continuous distribution of components. The expansion is based on the assumption that the microscopic parameters characterizing the system may be expressed as those of a reference system plus a series of "small'' corrections. Explicit formulas for the first- and second-order solutions to the equilibrium and critical-point conditions are given. The low-order perturbation solutions will be useful when the phase boundaries of the system are close to those of the reference system.
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    The Journal of Chemical Physics 87 (1987), S. 5437-5448 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The self-diffusivity of Brownian hard spheres in a simple shear flow is studied by numerical simulation. Particle trajectories are calculated by Stokesian dynamics, with an accurate representation of the suspension hydrodynamics that includes both many-body interactions and lubrication. The simulations are of a monolayer of identical spheres as a function of the Péclet number: Pe =γ(overdot)a2/D0, which measures the relative importance of shear and Brownian forces. Here γ(overdot) is the shear rate, a the particle radius, and D0 the diffusion coefficient of a single sphere at infinite dilution. In the absence of shear, using only hydrodynamic interactions, the simulations reproduce the pair-distribution function of the equivalent hard-disk system. Both short- and long-time self-diffusivities are determined as a function of the Péclet number. The results show a clear transition from a Brownian motion dominated regime (Pe〈1) to a hydrodynamically dominated regime (Pe〉10) with a dramatic change in the behavior of the long-time self-diffusivity.
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    The Journal of Chemical Physics 87 (1987), S. 4324-4331 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: This study demonstrates the mutual orientation of three tensor interactions in a single NMR experiment. The orientation of the 15N chemical shift tensor relative to the molecular frame has thus been determined in polycrystalline L-[1-13C] alanyl-L-[15N] alanine. The 13C–15N and 15N–1H dipole interactions are determined using the 1H dipole-modulated, 13C dipole-coupled 15N spectrum obtained as a transform of the data in t2. From simulations of the experimental spectra, two sets of polar angles have been determined relating the 13C–15N and 15N–1H dipoles to the 15N chemical shift tensor. The values determined are βCN =106°, αCN =5° and βNH =−19°, αNH =12°. The experiment verifies, without reference to single crystal data, that σ33 lies in the peptide plane and σ22 is nearly perpendicular to the plane.
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    The Journal of Chemical Physics 87 (1987), S. 4310-4314 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The C˜→A˜ emission spectra for H2O and D2O are measured and calculated. The theoretical model is based on an exact treatment of the dissociation dynamics of the A˜ state using a calculated potential energy surface. Agreement with the measurements is excellent. The spectra extend from λ∼380 nm up to λ∼600 nm with maxima around 425 (H2O) and 440 nm (D2O).
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  • 39
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    The Journal of Chemical Physics 87 (1987), S. 4302-4309 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We have recorded the photoelectron (photodetachment) spectra of the gas-phase negative cluster ions NO−(N2 O)1 and NO−(N2 O)2 using 2.540 eV photons. Both spectra exhibit structured photoelectron spectral patterns which strongly resemble that of free NO−, but which are shifted to successively lower electron kinetic energies with their individual peaks broadened. Each of these spectra is interpreted in terms of a largely intact NO−subion which is solvated and stabilized by nitrous oxide. For both NO−(N2 O)1 and NO−(N2 O)2, the ion–solvent dissociation energies for the loss of single N2 O solvent molecules were determined to be ∼0.2 eV. Electron affinities were also determined and found to increase with cluster size. The localization of the cluster ion's excess negative charge onto its nitric oxide rather than its nitrous oxide subunit is discussed in terms of kinetic factors and a possible barrier between the two forms of the solvated ion.
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  • 40
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    The Journal of Chemical Physics 87 (1987), S. 4315-4323 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The lowest excited triplet state and the sublevel dynamics have been studied in 1, 5-naphtho-22-crown-6 (I), 1,8-naphtho-21-crown-6 (II), and 2, 3-naphtho-20-crown-6 (III) and their complexes with various metal ions (Na+, K+,Cs+, Tl+) using optical detection of magnetic resonance at 1.2 K in zero applied magnetic field. The results indicate that the orientation of the heavy ion perturber with respect to the naphthalene chromophore selectively influences both the sublevel radiative rates and their populating rates by intersystem crossing. The largest heavy atom effect results when the metal ion perturber is located along the out-of-plane axis originating from the center of the naphthalene chromophore (I). The selective effects on the sublevel dynamics can be explained in terms of symmetry restrictions which enter the spin–orbit matrix elements via overlap integrals between the pi electrons of naphthalene and the p orbitals of the heavy atom.
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    The Journal of Chemical Physics 87 (1987), S. 4332-4338 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The rotational spectrum of v=0 and v=1 X 3Σ− SH+ was measured by laser magnetic resonance. Rotationally cold (Tr=30 K), vibrationally excited (Tv=3000 K) ions were generated in a corona excited supersonic expansion. The use of this source to identify ion signals is described. Improved molecular parameters were obtained; term values are presented from which astrophysically important transitions may be calculated. Accurate hyperfine parameters for both vibrational levels were determined and the vibrational dependence of the Fermi contact interaction was resolved. The hyperfine parameters agree well with recent many-body perturbation theory calculations.
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    The Journal of Chemical Physics 87 (1987), S. 4339-4343 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We propose a theory for the influence of conformational dynamics of solvated macromolecules on the translational self-correlation functions and associated laser light scattering spectra of the solution in an external electric field. This theory assumes that the electrophoretic drift velocity of a macroion may be coupled to its internal degrees of freedom via an unspecified auxiliary stochastic process to which we refer as "electrophoretic mobility fluctuations.'' A surprisingly diverse set of fluctuation-generated spectral signatures, which depend strongly on the underlying statistical model, emerge from the analysis. These effects range from skewed Lorentzian profiles to satellite lines having a field-dependent amplitude.
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    The Journal of Chemical Physics 87 (1987), S. 4344-4360 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: It is proposed that Rydberg and valence σ* conjugate orbitals have separate existences and can be seen in the same spectrum if the σ* MO can be disentangled from the Rydberg manifold. Because the energy of the σ* MO is a consequence of the σ–σ* split resulting from bond formation, the spectra of molecules having weak bonds should show low-lying transitions to σ* in addition to the conjugate Rydberg bands. Inelastic electron scattering spectra in the x-ray region (270–730 eV) of molecules having bond strengths in the 20–50 kcal/mol regime clearly show well-isolated transitions to low-lying σ* MOs, and in some cases the simultaneous presence of virtual σ* and Rydberg conjugate orbitals. The general characteristics of excitations from C 1s, O 1s, and F 1s inner orbitals to σ* MOs are listed and illustrated by the x-ray spectra of several compounds in which the weak bond involves the O–O or O–F linkage. Quantitative inner-shell optical oscillator strengths derived from the energy loss spectra are reported for H2O, F2O, CF3OF, CF3O2CF3, (CH3)3COH, and (CH3)3CO2C(CH3)3. The valence-shell spectrum of F2O also has been determined. Low-lying inner-shell excitations to σ* valence MOs are identified by their relatively large term values and oscillator strengths. The term values of transitions to σ* MOs in weak-bond molecules correlate with the relevant bond lengths when considered together with the sum of the atomic numbers of the atoms forming the weak bonds.
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    The Journal of Chemical Physics 87 (1987), S. 4368-4370 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution infrared absorption spectra have been recorded for the ν4 vibrational mode of CD4 trapped in solid argon and krypton. As with CH4, evidence for two dominant sites was found: one with a cubic close-packed (CCP) environment and the other with a hexagonal close-packed (HCP) environment. The fine structure for the CCP site resembles that for a tetrahedral molecule rotating in an octahedral field: singlet peaks for P(1), Q(1), and R(0), and a doublet for R(1). The fine structure for the HCP site is more complex and is not assigned to specific rotational transitions. By high temperature annealing it was possible to eliminate the HCP site completely with increase in concentration of the more stable CCP site. The slow relaxation of nuclear spin found for CH4, from an F state (J=1) to an A state (J=0), was found to be two orders of magnitude faster for CD4.
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    The Journal of Chemical Physics 87 (1987), S. 4361-4367 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Temperature dependence of the emission spectrum of 1,4-naphthoquinone has been investigated in the vapor phase as well as in degassed carbon tetrachloride. It is shown that the emission consists of the dual phosphorescence from T1(n,π*) and T2(n,π*), in addition to the weak delayed fluorescence from S1(n,π*). The occurrence of the T2 phosphorescence is caused by the thermal population from T1. In the vapor phase the T1 and T2 phosphorescence origins are determined to be, respectively, 20 295 and 20 475 cm−1. These observations lead to the conclusion that the weak absorption band at near 490 nm is attributed to the S0→T2 transition. It is indicated that the T2 state has a symmetry of A2.
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    The Journal of Chemical Physics 87 (1987), S. 4371-4375 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared spectroscopy, fluorescence, and incoherent saturation experiments have been performed on matrix-isolated BH2D−2. We find that the 942 cm−1 vibrational mode of this molecule in KBr is unsaturable up to laser pump intensities of 1 MW/cm2 in marked contrast with the earlier measurements on ReO−4, which give a saturation intensity of 55 W/cm2. The different behavior for the light molecule is a result of one-phonon decay to a nearby lower-lying internal vibrational mode. Because of the small moment of inertia of the molecule high frequency librational modes provide a third-order decay channel between this lowest frequency internal vibrational mode and the ground state.
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    The Journal of Chemical Physics 87 (1987), S. 4383-4387 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The Ar3–HCl tetramer has been identified via the observation of its microwave rotational spectrum using the pulsed nozzle Fourier transform technique. The rotational spectroscopic constants of the ground vibrational state have been obtained for the 35Cl/37Cl isotopes from measurements of the J=1→2 to J=4→5 transitions and their hyperfine structure. For Ar3–H35Cl, the values found for B0, DJ, DJK, and χaa are 843.8974(1) MHz, 2.333(2) and 1.818(6) kHz, and 31.006(5) MHz, respectively, and for Ar3–H37Cl, 825.9811(2) MHz, 2.211(5) and 1.940(12) kHz, and 24.481(8) MHz. The cluster is a symmetric top with the HCl along the C3 axis, its H end directed towards the Ar3 trimer. In its torsional oscillations, the HCl makes an average angle of 36.91° with the symmetry axis. The chlorine isotopic substitution leads to values of 3.8510 and 4.0024 A(ring) for the Ar–Ar and Ar–Cl distances. The results of the present study are compared with those reported earlier for the Arm–HF (m=1,2,3) and Arm–HCl (m=1,2) clusters.
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    The Journal of Chemical Physics 87 (1987), S. 4376-4382 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We have performed an infrared fluorescence study on the intramolecular vibrational relaxation (IVR) from C–H stretch fundamentals in isolated ground state polyatomic molecules. It was found that a density of about 70 combined rotational–vibrational states of a common J and symmetry species per cm−1 is needed to ensure that complex state mixing and IVR occur, although we observed a substantial range of couplings for initial states of the same molecule at higher state densities above the threshold. Propynal was studied as an example of a molecule with a low state density. Fluorescence from propynal shows that although there is substantial state mixing, it is best described as a complicated case of Fermi resonance and Coriolis coupling, as in smaller molecules rather than the multistate mixing seen in larger ones. Infrared fluorescence from terminal C–H stretches of some acetylene derivatives was also measured; these show a slight difference in the extent of IVR from other C–H stretches. Molecules were cooled and isolated in supersonic molecular beams and excited in the C–H stretch region with an optical parametric oscillator. Fluorescence spectra were recorded with either a circular variable filter machine or a cryogenic Michelson interferometer.
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    The Journal of Chemical Physics 87 (1987), S. 4388-4394 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence site selection spectra of Zn-substituted cytochrome c and Zn-mesoporphyrin were measured as a function of excitation energy and temperature within 5–60 K. The emission energies determined for Zn-cytochrome c were comparable with those of Zn-mesoporphyrin and mesoporphyrin in polar glassy matrices and with resonance Raman spectra of heme proteins. In the site selection spectra of both Zn-cytochrome c and Zn-mesoporphyrin in polar organic glass an increase in the intensity of zero phonon emission lines was observed with an increase of temperature between 5 and 30 K. The irregular spectral changes were interpreted on the basis of the temperature dependence of the linewidth as well as possible hole-burning phenomena.
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    The Journal of Chemical Physics 87 (1987), S. 4395-4398 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A powerful method for detailed studies of the static and dynamic properties of molecules in highly excited vibrational states is presented. NH3 molecule is excited to the v=5 state in the N–H stretching mode by a pulsed dye laser and a subsequent transient change in the millimeter wave absorption due to the inversion transition in the excited state is observed before the distribution returns to thermal equilibrium. The determined inversion transition frequencies are more accurate by more than two digits than those reported in the previous work.
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    The Journal of Chemical Physics 87 (1987), S. 4399-4405 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The possible effects of exchange processes upon polarized ESR spectra are discussed using the amended Bloch equations. The results are applied to an analysis of the polarized ESR spectrum of the cyclohex-1-olyl radical, observed over a range of temperatures using the time integration spectroscopy technique. The spectrum obtained at 223 K displays an unusual E/A/E/A polarization pattern, the full analysis of which is given. In the light of these results, the fact that the polarized ESR spectra of radical anions usually fail to show any radical pair mechanism polarization is discussed.
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    The Journal of Chemical Physics 87 (1987), S. 4406-4408 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: It is shown that the theory of Sogami and Ise leading to an attraction between particles with charges of the same sign contains errors. When the errors are corrected the calculated attraction disappears.
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    The Journal of Chemical Physics 87 (1987), S. 4423-4428 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The three photon resonant, four photon ionization spectra of D2 via the C 1Πu, v′=0–4 levels are reported. The photoelectron spectra for all five bands and the photoelectron angular distribution via the C 1Πu, v′=0–3←X 1∑+g, v″=0, Q(3) transitions are also reported. The photoelectron spectra are compared with theoretical Franck–Condon factors determined using accurate potential curves for the D2 C 1πu and D+2 X 2∑+g states. As in the case of H2, the photoelectron spectra display non-Franck–Condon behavior, and the photoelectron angular distributions exhibit strong v+ dependences. The relation of the present results to earlier results on H2 is discussed.
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    The Journal of Chemical Physics 87 (1987), S. 4429-4434 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: During excitation with ultraviolet light, polydiacetylene crystals show a photoinduced absorption which is ascribed to a triplet excited state of the individual polymer chains. We have measured this absorption using partially and fully polymerized TS and FBS single crystals. The results of stationary and time-resolved experiments are discussed.
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  • 55
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    The Journal of Chemical Physics 87 (1987), S. 4419-4422 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A formalism is developed to predict the relative absorption and circular dichroism intensities for the symmetric and antisymmetric bending vibrations of A2B2 molecules belonging to C2 symmetry. Predictions for three different situations are as follows: (a) when partial charges are assumed to follow the nuclei and contributions from the charge reorganization during the vibrations are negligible, the dissymmetry factor for symmetric bending vibration is about two orders of magnitude larger than that for antisymmetric bending vibration with opposite sign; (b) when the fixed partial charge contributions are negligible and charge flow along the B–B bond is of the same order as that along A–B bond, for molecules with ∼60° dihedral angle the dissymmetry factors for symmetric and antisymmetric bending vibrations are of nearly equal magnitudes with opposite signs; (c) when the fixed partial charge contributions are negligible and the charge flow along A–B bond is much greater than that along B–B bond the dissymmetry factors follow a simple relation. The latter two points are also applicable to the symmetric and antisymmetric A–B stretching vibrations.
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  • 56
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    The Journal of Chemical Physics 87 (1987), S. 4409-4418 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Spectroscopic properties have been calculated for the diatomics BCl, CS, CCl+, BF, CO, CF+, N2, CN−, and NO+ by Møller–Plesset many-body perturbation theory through MP4SDQ (fourth order with single, double, and quadruple substitutions). Very good agreement of both rotational and vibrational constant predictions with experiment was found at the MP4SDQ level of theory with the extended basis sets used (66 CGTO's). CI dipole moments, which appear to be accurate to at least 0.1 D, and electric field gradients, which yield eq0Q values accurate to within 1–2 MHz, were obtained.
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  • 57
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    The Journal of Chemical Physics 87 (1987), S. 4435-4446 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The first experimental observation of laser induced fluorescence from the furan cation, C4H4O+, is reported. The ion is formed in a supersonic free jet via a two photon ionization involving the 193 nm output of an ArF excimer laser. The B˜→X˜ electronic transition is probed and vibrational assignments are presented for both states. Comparisons to the infrared, Raman, multiphoton ionization, and photoelectron spectrum of the parent molecule are made. The term value T00 for the B˜→X˜ electronic transition is located at 24 675 cm−1, which differs drastically with previously reported values from both experimental and theoretical investigations. These differences are discussed and probable explanations proposed. The lifetime of the vibrationless level of the B˜ state is measured to be 330 ns.
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    The Journal of Chemical Physics 87 (1987), S. 4447-4455 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The microwave spectrum of the Ar⋅⋅⋅vinyl cyanide van der Waals complex has been observed using a pulsed Fourier transform microwave spectrometer. Two vibrational states have been identified. Centrifugal distortion and 14N quadrupole hyperfine analyses of the observed transitions have been performed for both states. The lower (ground) state fits an asymmetrical top Hamiltonian significantly better than the upper state. The two states are believed to arise because of a tunneling motion within the complex. The preferred structure of the complex has the Ar atom located approximately equidistant from the methylene carbon and nitrogen atoms and ∼34° out of the plane of the vinyl cyanide subunit.
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  • 59
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    The Journal of Chemical Physics 87 (1987), S. 4465-4470 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Pure rotational transitions of allene in the degenerate vibrational states v9=1, v10=1, and v11=1 have been observed with a pulsed microwave Fourier transform spectrometer. The assignment of the J=0→1 transitions was confirmed by microwave–microwave double resonance experiments. From the latter and from Stark effect measurements the magnitude of the vibrationally induced dipole moments have been determined. The rotational constants known from high-resolution infrared spectra have been improved.
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  • 60
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    The Journal of Chemical Physics 87 (1987), S. 4456-4464 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The equilibrium orientation and the kinetics of reorientation of NH3D+ dilute in a number of Tutton salts and in ammonium sulfate have been studied. The kinetics of reorientation are very slow (hours or days) at 4 K and consequently it is difficult to obtain the equilibrium distribution. Our previous report of a maximum extent of orientation at about 30 K is incorrect. Instead the extent of orientation increases monotonically as the temperature is lowered. This can be modeled with NH3D+ ions interacting by means of their dipole moments. Although the salts behave as well defined phases at low temperatures, the possibility of glass-like behavior remains open for both the salts and the Monte Carlo simulation. The kinetic processes occur by tunneling, and the tunneling rates have been measured. These rates give reasonable values for the barrier to reorientation. The orientation rate is accelerated by broadband infrared irradiation of the sample. The radiation is probably absorbed by the N–D stretches and induces the rotation of the excited ions.
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    The Journal of Chemical Physics 87 (1987), S. 4471-4477 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Excitation spectra for narrow Raman lines and a broad luminescence band have been measured in β-carotene in isopentane at 177 K over a wide spectral range on the low-energy side of the 1Ag–1Bu absorption band. The result has been found to be well explained by a stochastic theory that takes into account the finiteness of the correlation time for the intermediate-state interaction. Various parameters, such as the magnitude and the rate of the energy modulation in the intermediate state, have been determined from the analysis of the excitation profiles. The parameter values obtained indicate that the intermediate-state interaction is far from the motional-narrowing limit in this system.
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  • 62
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    The Journal of Chemical Physics 87 (1987), S. 4478-4486 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Observation of the 2ν1 overtone band in the hydrogen-bonded complex HCN---HF permits evaluation of the anharmonicity constant X11=−116.9(1) cm−1 and determination of the anharmonicity corrected fundamental frequency ω1. This information, and available data from previous rovibrational analyses in the common and perdeuterated isotopic species of HCN---HF, offer an opportunity for calculation of an approximate stretching harmonic force field. With the assumptions f12=f24=0.0, the remaining force constants (in mdyn/A(ring)) are evaluated as: f11=8.600(20), f22=6.228(9), f33=19.115(40), f44=0.2413(39), f13=0.000(13), f14=0.0343(2), f23=−0.211(6), f34=0.000(2). These compare to f11=9.658(2) in the HF monomer and f11=6.244(3) and f33=18.707(16) in the HCN monomer. These results provide the information necessary to quantitatively assess the applicability of the Cummings and Wood approximation in this hydrogen-bonded complex and also give an estimate of Dej, the equilibrium distortion constant in the harmonic limit. Comparisons of these experimentally determined parameters with the predictions of ab initio molecular orbital calculations at several levels of approximation are presented.
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    The Journal of Chemical Physics 87 (1987), S. 4498-4509 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Resonance rotational hyper-Raman scattering cross sections excited by identical linearly polarized incident photons are derived for symmetric tops. In the absence of pure dephasing, the rotational structure of a RHR vibrational transition is described, in general, by five scattering invariants which are derived in an irreducible tensor framework. The pattern of relative rotational RHR intensities is a sensitive function of the two-photon resonant vibronic state dephasing constant. High quality rotational RHR spectra of NH3 are obtained using blue incident radiation at half the X˜→A˜ transition energy. Fits to the observed patterns of relative rotational RHR intensities determine lifetimes of 38, 60, and 100 fs for the v′2 =1,2,3 A˜ state vibronic bands respectively. Although seven rotational branches (N,O,P,Q,R,S,T) are possible in HR, only three (P,Q,R) are observed in these RHR spectra of ammonia due to the magnitude and relative signs of vibronic matrix elements in the scattering cross section expressions.
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    The Journal of Chemical Physics 87 (1987), S. 4487-4497 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Raman and infrared spectra of neat n-hexadecane were measured as a function of hydrostatic pressure up to 54 and 83 kbar, respectively. The application of high pressure leads to anomalous frequency shifts and band splittings, and induces drastic changes in the band shapes and in the distribution of intensities within the spectra. The pressure-induced changes in the vibrational spectra of n-hexadecane are discussed in terms of phase transitions, molecular distortions, interchain interactions, frequency dispersions, and Fermi resonance interactions. The effect of pressure on the Raman and infrared spectra of n-hexadecane is used to test conclusions drawn from theoretical Fermi resonance calculations concerning the origin of several features in the Raman spectra of n-alkanes. Evidence is given to show that some assumptions made in these calculations are incorrect and that the model used is too simple to account for the intensity distribution in the CH stretching region of the Raman spectra of n-alkanes. It is also shown that the peak heights of the 2930 and 2850 cm−1 Raman bands can be affected by such factors as the magnitude of interchain interactions which renders questionable the use of the peak height ratio between these bands for the quantitative estimation of the gauche/trans population in biomembranes and polymers. While hydrostatic pressure initially causes a conformational ordering of the chains in n-hexadecane, at high pressures the compression along the chain direction is predominant over the lateral compression, leading to a distortion of the methyl end groups and a conformational disordering of the methylene chains.
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    The Journal of Chemical Physics 87 (1987), S. 4510-4518 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The three title electron-impact techniques are used to study the ground and excited states of acetylene negative ion and their decay processes. The π* resonance at 2.6 eV predissociates into C2H− and H. Four narrow resonances are observed in the transmission spectrum in the 7.5–9.5 eV region and assigned to Feshbach and core-excited shape resonances with double occupation of Rydberg orbitals and ground state positive ion core. These four resonances decay into low-lying Rydberg states of neutral acetylene, the first two undergo quasiresonant autodetachment ejecting low energy (〈0.7 eV) electrons, and the lowest also dissociates to yield C−2. One additional resonance is observed in the C−2 yield, which is not observable in other decay channels. The shapes of the dissociative attachment bands differ qualitatively from the band shapes of the parent and grandparent states, indicating either a strong v dependence of the dissociation rate or the admixture of σ* orbitals in some of the dissociating anion states.
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    The Journal of Chemical Physics 87 (1987), S. 4519-4531 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Discretization (with localized basis functions or grid points) of the coupled integral equations for molecular collisions leads to a very large system of linear algebraic equations. New methods, which are well adapted to vector supercomputers and parallel architectures, are developed for solving this large system. The multilevel adaptive technique (MLAT) is combined with recursive and iterative techniques. First, a multichannel solution is obtained on a low level grid. The basis is then adapted to this solution and the coarse solution is projected or interpolated onto the adapted basis. The scattering amplitudes (K-matrix elements) on the high level are then developed through use of either the recursion method (for single amplitudes, or a small batch of them) or the iterative technique (for all transitions from a specified initial state). In both of these methods, the original large system of algebraic equations is projected into a much smaller subspace (an orthonormalized Krylov space) spanned by a few basis vectors. Applications to very large systems are possible because it is not necessary to store or invert a large matrix. Computational results on a model chemical reaction are presented.
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    The Journal of Chemical Physics 87 (1987), S. 4532-4539 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Trajectory surface hopping calculations were performed on optimized diatomics-in-molecules surfaces to study Na(2P) collisions with H2 and D2 molecules (v=0, j=1) at four different translational energies (0.039, 0.062, 0.101, and 0.140 eV). Two methods were used to predict surface hopping: (1) transformation of the multidimensional surface intersection to a local one-dimensional curve crossing and calculation of the Landau–Zener transition probability, and (2) integration of the coefficients of the adiabatic electronic states to determine transition probability. For all initial conditions used in this work, we found that method (2) gave significantly larger quenching cross sections. Also in this paper we present results that show nonadiabatic coupling terms calculated by the diatomics-in-molecules method are in good agreement with ab initio values.
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    The Journal of Chemical Physics 87 (1987), S. 4540-4545 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We have measured the absolute cross section value and emission linewidths of the OI (3s5S0–3p5P; λ7774 A(ring)) multiplet excited by electron impact on O2. The 3p5P cross section, which was measured from threshold to 400 eV, is large, with a value of 4.23×10−18 cm2 ±14% measured at 100 eV, hence this cascade feature constitutes a significant source of excitation for the OI (5S0) state. The multiplet's emission line widths are highly Doppler broadened in dissociative excitation, and display two distinct kinetic energy distributions. These distributions indicate that both purely repulsive and discrete, bound, excited molecular states which then predissociate are involved in the dissociation process leading to the excitation of OI λ7774 A(ring). The magnitude of the measured cross section, and the fragment kinetic energy distribution inferred from the observed Doppler broadening both indicate that previous time-of-flight studies of the metastable OI (5S0) state require some reinterpretation.
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    The Journal of Chemical Physics 87 (1987), S. 4546-4558 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of F(2P)+ketene and F(2P)+ketene-d2 were studied in a flow reactor. Spectra of the radical products CH2F, CD2F, CH, CF, and atomic carbon were detected between 292–395 nm by resonance enhanced multiphoton ionization (REMPI) mass spectrometry. Fluoromethyl radicals were identified as a major product of the F+ketene elementary reaction. REMPI spectra of fluoromethyl radicals originated from two-photon preparation of 3p, 4p, and 5p Rydberg states (quantum defect ∼0.6). Absorption of a third laser photon ionized the radicals, a 2+1 REMPI mechanism. Rydberg band origins were observed in CH2F at ν00=52 863, 63 275, and 67 265 cm−1 and in CD2F at ν00=52 786, 63 195, and 67 186 cm−1. A normal mode analysis revealed the vibrational frequencies of the C–F stretch, CH2 scissors, and out-of-plane bending modes in the Rydberg states. The ground state out-of-plane bending frequency in CH2F is 260(30) cm−1 and in CD2F it is 170(30) cm−1. CH radicals were generated by the photolysis of ketene and observed at ∼311 nm by two-photon excitation through the D 2Π(v′=2) ←←X 2Πr band. The reaction mechanism that generated the CF radicals was not determined. The REMPI CF radical spectrum generated by a 2+1 photon mechanism appeared as a series of bandheads described by the constants ν00=∼52 572 cm−1, ωe =1820 cm−1, and ωexe =−18.2 cm−1.
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    The Journal of Chemical Physics 87 (1987), S. 4559-4575 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A theory of the vibrational energy relaxation of a symmetric top molecule trapped in a rare gas matrix is presented. The direct relaxation mechanisms of the energy on the molecular orientation and on the lattice vibrations (including the local modes) are described within the framework of the nonadiabatic coupling between the internal vibrational mode of the molecule and the low-frequency external modes. The three types of relaxation constants are analyzed. The transfer to the orientational modes of the molecule is shown to be the more efficient since the corresponding relaxation time ranges between 1 μs and 50 ns, according to the nature of the rare gas matrix and to the temperature. The multiphonon relaxation constant is calculated for two specific deexcitation channels. The phonon multimode process provides relaxation times which range between 1 ms and 10 μs. Such a process is a characteristic of the nonadiabatic treatment of the total Hamiltonian. In contrast, the multiphonon monomode process, where the vibrational energy is transferred to the vibration of the center of mass of the molecule, gives larger relaxation times around 1 ms. This process is connected to the high orders in the interaction potential anharmonicity. The third species of relaxation constant which mix the orientational and translational processes is also analyzed for various typical relaxation channels. The corresponding relaxation times are one order of magnitude longer than those obtained from the multiphonon mechanisms. The calculated relaxation times are close to the experimental measurements and exhibit the same trends with rare gas changes and temperature rises.
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    The Journal of Chemical Physics 87 (1987), S. 4576-4588 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Kinetics associated with the decay of low lying excited states of argon is investigated in a pressure range up to 4×106 Pa. Selective pulsed vacuum-ultraviolet excitation is used for the first time for a kinetic study of argon allowing a rather detailed analysis. The results are deduced from time resolved total luminescence of the well-known second continuum which is associated with the lowest excimer states 0+u(3P1) and 1u, 0−u(3P2), having fast and slow radiative decays, respectively. A different ratio of the fast to the slow component is observed when exciting in the high or in the low energy side of the first self-broadened line, the 1S0→3P1 transition centered at 106.6 nm, quite similar to what has been reported for xenon. The kinetic model introduced by Wenck et al. for xenon [Chem. Phys. Lett. 66, 138 (1979)] is the only one that agrees with the observed time and pressure dependences. In this model, the decay of the atomic state 3P1 leads to efficient population of 1u, 0−u(3P2), via 0+u(3P1), and 1g, 0−g(3P2), molecular states and the atomic state 3P2. The radiative lifetime of the (1u, 0−u) excimer state is presently determined to be 3.15(5) μs. The decay associated with 1P1 excitation is more complicated since it involves more intermediate steps. No difference is detected when exciting in the low or in the high energy side of the corresponding self-broadened line. That result, together with the time behavior, allows one to conclude that the atomic state 3P0 is efficiently populated in the decay sequence, thus introducing a rather long lived reservoir effect. Such an effect is totally different from what was reported for xenon in which collision coupling with the nearby 6p levels plays a major role.
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    The Journal of Chemical Physics 87 (1987), S. 4589-4597 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Fragmentation mechanisms of the methyl formate and methyl formate-d1 ions have been investigated using threshold photoelectron–photoion coincidence (TPEPICO) mass spectrometry. The breakdown diagrams and ion kinetic energies of fragment ions were measured at internal energies of the molecular ion from 0 to 7 eV, and fragmentation pathways were elucidated. The formation of HCO+ showed a large kinetic isotope effect. The formation of CH3O+ from methyl formate-d1 is accompanied by a large kinetic energy release, about twice that calculated using quasiequilibrium theory (QET). Its relative abundance in the breakdown curve also appears to be inconsistent with statistical theory. Direct dissociation from an isolated state of the molecular ion was one possible explanation. Slow dissociations were observed for the formation of methanol ions resulting from a migration of the formyl hydrogen while QET predicts no metastable dissociation for this process. Two-component reaction rates for methanol ion formation suggest participation of more than one state or isomer. The heat of formation of HCOO was found to be −40±6 kcal/mol, indicating that it is less stable than COOH (ΔHf =−58+4 kcal/mol).
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    The Journal of Chemical Physics 87 (1987), S. 4598-4605 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Time domain absorption spectroscopy using a tunable, infrared diode laser has been used to monitor the vibrational excitation of CO2 produced in the 193 nm excimer laser photolysis of gas phase pyruvic acid (CH3COCOOH). Nascent vibrational populations were measured in the following ten vibrational states of CO2: 0000, 0110, 0220, 0330, 0440, 0001, 0002, 0003, 0111, and 0221. Approximately 97% of the CO2 photoproduct is observed to be directly formed in the vibrational ground state. The remaining molecules are formed with a significant degree of vibrational excitation, having mode temperatures T(ν2)=1800±150 K, T(ν3)=3700 ±1000 K, T(ν2+ν3)=2000±400 K. The present experimental data suggest that the 193 nm photolysis may proceed through more than a single dissociation channel and involve a number of different photofragments.
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    The Journal of Chemical Physics 87 (1987), S. 4612-4614 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: Recent upper and lower bounds established by the authors for the rate to diffuse to traps in a random medium are compared in a consistent manner by taking account of how the trap-free volume affects various definitions of the rate constant.
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    The Journal of Chemical Physics 87 (1987), S. 4606-4611 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: A kinetic study is presented of the reaction between lithium atoms and hydrogen chloride over the temperature range 700–1000 K. Li atoms are produced in an excess of HCl and He bath gas by pulsed photolysis of LiCl vapor. The concentration of the metal atoms is then monitored in real time by the technique of laser-induced fluorescence of Li atoms at λ=670.7 nm using a pulsed nitrogen-pumped dye laser and box-car integration of the fluorescence signal. Absolute second-order rate constants for this reaction have been measured at T=700, 750, 800, and 900 K. At T=1000 K the reverse reaction is sufficiently fast that equilibrium is rapidly established on the time scale of the experiment. A fit of the data between 700 and 900 K to the Arrhenius form, with 2σ errors calculated from the absolute errors in the rate constants, yields k(T)=(3.8±1.1)×10−10 exp[−(883±218)/T] cm3 molecule−1 s−1. This result is interpreted through a modified form of collision theory which is constrained to take account of the conservation of total angular momentum during the reaction. Thereby we obtain an estimate for the reaction energy threshold, E0=8.2±1.4 kJ mol−1 (where the error arises from uncertainty in the exothermicity of the reaction), in very good agreement with a crossed molecular beam study of the title reaction, and substantially lower than estimates of E0 from both semiempirical and ab initio calculations of the potential energy surface.
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    The Journal of Chemical Physics 87 (1987), S. 4615-4618 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The reactions of Ar+, N+, and Kr+ with SF6 have been investigated using a selected ion flow drift tube in the energy regime from thermal to a few eV relative kinetic energy of the reactants, KEcm, and the reaction of Xe+ with SF6 from 2 to 5 eV, KEcm, SF+5 is the dominant ionic product in all cases with the exception of the endoergic Xe+ reaction, where SF+3 was observed to be the product ion, the rate coefficient increasing dramatically with KEcm. The reaction involving Ar+ and N+ are fast (k∼10−9 cm3 s−1) and vary only slightly with energy. In the case of Kr+ the 2P3/2 state reacts fast (k∼6×10−10 cm3 s−1), while the 2P1/2 state is about an order of magnitude less reactive. The finding of the Kr+ (2P3/2) reaction leads to values AP (SF+5/SF6) ≤14.0 eV and D(SF5–F)=3.83±0.1 eV.
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    The Journal of Chemical Physics 87 (1987), S. 4622-4626 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: The relation between the fractal geometry of reactant trajectories and the rate of diffusion-controlled reactions is considered. A new possible mechanism for the effect of an external electric field on the rate of reactions is proposed on the basis of this consideration. The proposed mechanism predicts an increase in the rate constant with increasing electric field strength. Experiments in the literature which may be related with the proposed mechanism are surveyed. Finally directions in future extensions of the present study are suggested.
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    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 4619-4621 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A close-coupling channel computation of Ne*(3P0,2)–H2 (1∑+g, v=0) collisions, using the ab initio potentials given in a preceding paper, is reported. The molecule is considered as a rigid rotator. The autoionizing character of states dissociating into Ne* (2p53s)+H2 is ignored. Consequently Penning and chemi-ionizations are not considered. Combined fine structure and rotational transitions are the only inelastic channels expected. By means of a deflation procedure, collision channels leading to Ne*(1P1) are shown to be negligible in the present energy range (E≤175 meV). The "fragment'' basis (i.e., Ne*+H2 at infinite R) is adapted to the collision treatment since all off-diagonal elements of the electronic Hamiltonian, including the spin–orbit interaction (static couplings) are small. The coupling of angular momenta ( j1=0,1,2 of Ne*, j2=0,2 of para-H2, 1 of ortho-H2, l for the relative motion) leads to 27 coupled equations for ortho-H2 and 54 equations for para-H2, for each value of the total angular momentum J. These equations are solved by using the algorithm of Gordon, and the 81×81 S matrix is derived. The rotational excitation ( j2=0→2) probability takes a maximum value of the order of 10−2 at J≈15.
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  • 79
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    The Journal of Chemical Physics 87 (1987), S. 4634-4640 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The collisional quenching of NF(b 1Σ) by F2, IF, and I2 has been studied over the temperature range of 330 through 572 K. The extent of reaction was monitored by measurement of the emission intensity in the b→X transition near 529 nm. A laser-induced fluorescence technique was used to monitor the concentration of the transient species IF and to estimate the gas temperature. Essentially, the data shows that IF and I2 reactively quench NF(b 1Σ) at a gas kinetic rate proportional to T1/2 while F2 quenches less effectively by a factor of 20. At 300 K, the rate constants are 1.2×10−10, 1.4×10−10, and 4.4×10−12 cm3 s−1 for IF, I2, and F2, respectively. These results are correlated with the results of others to give estimates of the product branching ratio for formation of the electronically excited halogen molecules at elevated temperatures.
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  • 80
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    The Journal of Chemical Physics 87 (1987), S. 4627-4633 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation of H2O and D2O in the second band (λ(approximately-greater-than)120 nm) is investigated using two-dimensional (translation and rotation) classical trajectories. The calculations include all electronic states which are involved in the dissociation dynamics, i.e., B˜ 1A1, X˜ 1A1, and A˜ 1B1. The nonadiabatic transitions B˜→X˜ and B˜→A˜ near linearity are modeled in a very simple way, which does not yield the OH(2Σ)/OH(2Π) branching ratio. The rotational distributions for OH(2Σ) and OD(2Σ) agree qualitatively very well with the measurements. They are highly inverted and peak close to the highest accessible state. Comparing the OH(2Π) rotational distributions with recent experimental results we conclude that B˜→X˜ is probably the main dissociation pathway, although contributions from a B˜→A˜ transition cannot be excluded. The OH(2Π) distribution is also highly inverted with a peak near j∼43 in excellent agreement with experiment. The majority of trajectories on all three potential energy surfaces is direct. The shape of the various rotational distributions is determined by the first step of the dissociation from the FC region up to linearity where the crossing to the X˜ or the A˜ state might occur. As envisioned a long time ago the strong angular force near the FC region on the B˜ potential energy surface is responsible for the extremely high degree of rotational excitation for OH(2Σ) as well as for OH(2Π).
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  • 81
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    The Journal of Chemical Physics 87 (1987), S. 4641-4643 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The effect of the Lamb shift upon the ionization potential of the He-like atoms in their ground states is analyzed. It is shown that the Lamb shift of the ground state of the He-like atom tends to twice the same quantity of the H-like atom of the same Z in its ground state when Z→∞. From this observation, it is supposed that the Lamb shift of a given state of an atom or an ion with more than one electron is made up of the one-electron contributions, which can be calculated with the well known formulas for the radiative corrections to the energy levels of one-electron atoms by introducing the concept of the effective nuclear charge. To confirm this supposition, it is shown that the radiative corrections for the energy levels of the 2 1,3S states of the He atom as well as for the fine structure splittings of the 2 3P and 3 3P states of the He atom can be understood along the same line. It is finally concluded that the effect of the Lamb shift upon the ionization potential or the excitation energy may have to be considered only if a 1s electron is involved either in the ionization or in the excitation.
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  • 82
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    The Journal of Chemical Physics 87 (1987), S. 4644-4650 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Relativistic molecular orbital calculations in the multiple scattering approximation are reported for silver tricarbonyl, and comparisons are made to optical absorption and electron spin resonance spectra. Spin–orbit effects are modelled through the Dirac scattered-wave (DSW) formalism. Spin–polarization effects are estimated from quasirelativistic spin-unrestricted calculations. The influence of different local density potentials on the spin distributions and hyperfine tensors are examined. The calculations show good agreement with optical spectral data and with the observed 107Ag and 13C hyperfine tensors. The use of relativistic exchange–correlation potentials in calculating spin-dependent properties leads to a slightly better agreement with experiment. The calculations predict that the unpaired electron in Ag(CO)3 has about 40% silver 5pz character.
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  • 83
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    The Journal of Chemical Physics 87 (1987), S. 4651-4664 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A three-dimensional quantum mechanical study of the (Ar+H2)+ system was carried out within the reactive infinite order sudden approximation. All three arrangement channels for exchange and charge transfer were treated simultaneously. Steric factors, opacity functions, angular distributions, and integral cross sections were calculated. Whenever possible, these were compared with both experimental and trajectory surface hopping (TSH) results. Whereas the fit with the TSH results was reasonable, the fit obtained with the experiment was less satisfactory. The reason for that can be attributed at least partially to the semiempirical DIM potential employed in the calculation.
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  • 84
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    The Journal of Chemical Physics 87 (1987), S. 4665-4672 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The radiative lifetime of the A 2Σ+(v′=0, N′=1) state of OH has been computed, using the theoretical potentials and transition moment, to be 673 ns, in excellent agreement with two of the experimental values (686±14 and 693±10 ns) determined by laser excitation fluorescence. The electron correlation treatment has been calibrated using full CI (FCI) calculations in a [4s3p2d/2s1p] Gaussian basis set. When a δ orbital is included in the CASSCF/MRCI treatment, the transition moment is within 0.2% of the FCI value. A basis set study shows that the [6s5p4d2f1g/4s3p2d] ANO basis set employed in our study is probably within 1% of the basis set limit for the transition moment. The theoretical radiative lifetimes, which are expected to be lower bounds and accurate to 2%, are sufficiently accurate to rule out the slightly lower value determined by Hanle effect studies, and the higher values determined for the v′=0 N′=1 level by the high frequency deflection technique (HFD). The HFD lifetimes for higher N′ values, however, are in relatively good agreement with theory.
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  • 85
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    The Journal of Chemical Physics 87 (1987), S. 5449-5456 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The density functional theory of freezing is used to study the liquid to crystal phase transition in the hard-sphere and Lennard-Jones systems. An important step in the calculation is the parametrization of the solid phase average single particle density ρ(r). In this work two popular parametrizations are compared. The first method is a general Fourier decomposition of the periodic solid density in which the amplitude of each (non-symmetry-related) Fourier component is treated as an independent parameter. The second parametrization, which is more restrictive but easier to implement, approximates the solid density as a sum of Gaussian peaks centered at the sites of a periodic lattice. The two methods give essentially identical results for the phase diagrams for the two systems studied, but the crystal density predicted by the Fourier method exhibits significant anisotropies which are excluded from the Gaussian representation by construction.
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  • 86
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    The Journal of Chemical Physics 87 (1987), S. 5457-5463 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Approximations commonly used to relate memory functions to time correlation functions governed by Newtonian dynamics are shown to be incorrect for strongly inhomogeneous systems. An exact expression for the space dependent diffusion coefficient is given in terms of time correlation functions whose dynamics are governed by Newton's equations. The resulting expression is evaluated using both the Bhatnagar–Gross–Krook kinetic equation and the Fokker–Planck equation to calculate the required time correlation functions for a system containing a specularly reflecting wall and for a system having a harmonic potential. For inhomogeneous systems, the memory function may not be approximated by the corresponding time correlation function. In addition, certain velocity correlations near a specularly reflecting wall are shown to contain a t−1/2 long time tail and a kinetic boundary layer whose thickness grows as t1/2; these features are absent from the memory function.
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  • 87
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    The Journal of Chemical Physics 87 (1987), S. 5464-5476 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Equilbrium properties of a rare-gas fluid contained between two parallel fcc(100) planes of rigidly fixed rare-gas atoms were computed by means of the grand-canonical ensemble Monte Carlo method. The singlet distribution function ρ(1), and the pair-correlation function g(2) in planes parallel to the solid layers, indicate that the structure of the pore fluid depends strongly on the distance h between the solid layers. As the separation increases from less than two atomic diameters, successive layers of fluid appear. The transitions between one and two layers and three and four layers are especially abrupt and are accompanied by changes in the character of g(2) from dense fluid-like to solid-like. Long-range, in-plane order in the fluid layers diminishes with increasing h, but is still evident in the contact layer (i.e., that nearest the solid layer) at h=16.5 atomic diameters, the largest separation considered. The structure of the contact layer reflects the solid-layer structure and differs significantly from the adjacent inner fluid layers, whose g(2) resembles that of the corresponding bulk fluid. Decreasing the density of atoms in the solid layers blunts the peaks in ρ(1) and g(2), although even for the least dense layer considered the contact layers of fluid evince long-range, in-plane order. Replacing the discrete pairwise fluid–solid interactions with the mean field resulting from smearing the solid atoms over the plane of the solid layer destroys the "phase transitions'' and the associated long-range, in-plane order.
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  • 88
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    The Journal of Chemical Physics 87 (1987), S. 5483-5496 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider the problem of modeling the thermodynamic behavior of a lipid bilayer using statistical mechanics. In this paper, we present Monte Carlo calculations of the single chain density of states appropriate to the mean field model of Pink et al., under a variety of assumptions on the time scales of various lipid motions. We find that Pink et al.'s density of states agrees qualitatively with our calculation. Our results also provide justification for assumptions in the density of states calculation of Jacobs et al.
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  • 89
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    The Journal of Chemical Physics 87 (1987), S. 5477-5482 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The structures of NaBr, KBr, RbBr, and CsBr in the vapor phase were determined via standard electron diffraction counting techniques with nozzle temperatures ranging from 820–920 K. The data analysis yielded the structure parameters and the ratio of the monomeric to dimeric compounds. The mean amplitudes of vibration for the monomeric molecules were held at values based on microwave frequencies and the harmonic potential approximations. The corrected monomer distances re agree well with microwave–spectroscopy results. Rhombic geometries with bonded dimer distances ranging from 2.74 to 3.37 A(ring) and Br–M–Br angles that ranged from 85° to 101.6° were observed. The percentage of dimer in the vapor was found to vary from 7% to 18%. The most surprising result was the large value obtained for the KBr dimer bonded distance. It is substantially larger than predicted by current theories and is nearly as large as the interionic distance in the crystal. Thermodynamic calculations were performed to allow comparisons of the dimer mole fractions observed with values derived from existing structure models.
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  • 90
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    The Journal of Chemical Physics 87 (1987), S. 5497-5503 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A two-dimensional quantum mechanical model is used to study the dissociative adsorption of H2 and its heavier isotopes on Ni(100). Dissociation probabilities are computed as a function of molecular kinetic energy for H2 , D2 , T2 , and a hypothetical heavier isotope. It is demonstrated how the variation of the zero point energy with mass strongly influences the dynamics. A qualitative agreement with recent experimental results for H2 and D2 is obtained. Quasiclassical trajectory calculations are performed for the same systems. By comparison with the exact quantum calculations, the classical probabilities for H2 and D2 are shown to be too large at low kinetic energies. For molecules heavier than T2 , classical dynamics are shown to be adequate. The sources of error in the classical simulations are discussed.
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  • 91
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    The Journal of Chemical Physics 87 (1987), S. 5512-5517 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The response of the mean square dipole moment 〈μ2〉 to chain expansion has been studied in a family of chains for which 〈r ⋅ μ〉0=0. Here r and μ are the end-to-end and dipole moment vectors, respectively, angle brackets denote the statistical mechanical average, and zero as a subscript denotes the ensemble unperturbed by long range interaction. For some of these chains, 〈μ2〉 increases upon chain expansion, while for other chains 〈μ2〉 decreases when the chain expands. At small expansion, the behavior is described by n0.43 (〈r2μ2〉0/〈r2〉0〈μ2〉0−1), where n denotes the number of bonds.
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  • 92
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    The Journal of Chemical Physics 87 (1987), S. 5518-5527 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Monolayer solids of CH4, CD4, and CF4 adsorbed on the basal plane surface of graphite are modeled with atom–atom interaction models and quasiharmonic lattice dynamics. Single molecule adsorption, the stability of registry lattices at monolayer condensation, and the stability of triangular tripod-down lattices relative to a denser monolayer packing are treated. The Novaco–McTague perturbation theory of the modulation of an incommensurate monolayer by the substrate is extended to molecular adsorbates with orientational degrees of freedom. Experimental data for monolayers of tetrahedral molecules on graphite are summarized; the model calculations give a fair account of the data, with some discrepancies in the energies of monolayer condensation.
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  • 93
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    The Journal of Chemical Physics 87 (1987), S. 5504-5511 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The phonon relaxation of the vibrational adbond of an adsorbed molecule and a phonon-damped adbond irradiated by a laser are studied. In the first half of the paper, approximations are made within the Zwanzig projection operator formalism in order to arrive at a master equation for the reduced density operator of a small subsystem (the adbond) in contact with a reservoir (the phonons). The conditions of validity for the Born and Markov approximations are derived. It is shown that the master equation is only valid for times t(very-much-greater-than)τc, where τc is the characteristic time of the reservoir. These results are then applied to the phonon relaxation of the vibrational adbond of physisorbed molecules. It is shown that for CO adsorbed on Ni or Cu (a strongly bound physisorbed system) the Born and Markov approximations are not justified. For the weakly bound system Ar on W, numerical results show that these approximations can be made. Finally, an adbond interacting with both laser radiation and lattice vibrations is considered. This system can be regarded as a subsystem (the adbond) in contact with two reservoirs, where the conditions for validity of the Markov approximation is then seen to be more severe than when each reservoir is considered independently. For the phonons, these conditions can never be matched. However, for an initial state given by an adbond in equilibrium with the lattice vibrations, the conditions for validity of the approximations prove to be the same as for the phonons and the laser considered independently.
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  • 94
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    The Journal of Chemical Physics 87 (1987), S. 5528-5533 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A metallurgical microscope is used to directly observe the two-dimensional structures of the binary mixtures of different sizes and specific gravities of monodisperse polystyrene spheres in sedimentation equilibrium and in deionized suspensions. When the sizes of small particles are smaller than 300 nm, large (diam 1.0 μm) and dense (specific gravity=1.5) spheres are often segregated upward by the ordered structures formed by the small less dense (specific gravity=1.05) spheres and Brownian movement of the larger spheres are restricted significantly. When the sizes of the small particles in the mixtures of large dense and small less dense particles are between 300 and 500 nm, the segregation effect is prevented and various kinds of "alloy'' structures of triangular, square, pentagonal, hexagonal, heptagonal, and octagonal patterns are observed. The interparticle distances between large–large, large–small, and small–small particles agree well with the effective sizes of spheres including the Debye-screening length. These results are consistent with the significant role of the electrical double layers under the influence of purely electrostatic repulsive forces in the effective hard-sphere model.
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    The Journal of Chemical Physics 87 (1987), S. 5534-5540 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We generalize a lattice field theory that formally provides an exact description of the statistical mechanical entropy of nonoverlapping flexible polymers to enable treatment of nearest-neighbor interaction energies. The theory is explicitly solved within an extended mean field approximation for a system of polymer chains and voids, and we also provide mean field results for polymer–solvent–void and binary blend–void mixtures. In addition to recovering the Flory–Huggins mean field approximation for these systems, our extended definition of the mean field approximation contains a set of corrections to Flory–Huggins theory in the form of an expansion in powers of the nearest-neighbor interaction energies.
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    The Journal of Chemical Physics 87 (1987), S. 5541-5553 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report on experimental and theoretical studies concerning the reaction kinetics of the solid state polymerization in diacetylene crystals. The individual reaction steps of the short-chain reaction intermediates (dimer, trimer, tetramer, ...) have been investigated by time resolved ESR and optical spectroscopy. In a microscopic theory energy barriers of molecular translations and rotations as well as the mismatch of the oligomer molecules in the crystal matrix are taken into account. The "molecular-mechanical'' model gained in this way is successful in describing the experimentally observed dependencies of the activation energy of the addition reaction on chain length, temperature, and conversion. It also explains the time-conversion behavior of the reaction. Moreover, we gain information about the activation energy of the total reaction and can anticipate the temperature dependency of the chain length.
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    The Journal of Chemical Physics 87 (1987), S. 5580-5580 
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    Topics: Physics , Chemistry and Pharmacology
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    The Journal of Chemical Physics 87 (1987), S. 5554-5561 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We have studied the infrared spectrum of ethylidyne, CCH3, chemisorbed on the Pt(111) surface over the temperature range 82 to 350 K. We observe three infrared active fundamentals: the C–C stretch at 1118 cm−1, the symmetric CH3 bend at 1339 cm−1, and the symmetric C–H stretch at 2884 cm−1. The absence of three other fundamentals in our spectra confirms that the molecule has C3v symmetry on the surface with the C–C axis oriented along the surface normal as had been determined from other studies. Our IR spectra demonstrate the strict validity of the surface dipole selection rules. We also observe a weak band at 2795 cm−1 which we attribute to the first overtone of the asymmetric CH3 bend at 1410 cm−1. The intensity of the overtone is enhanced by a Fermi resonance with the symmetric C–H stretch. At 82 K the symmetric bend has an unusually narrow intrinsic width of only 1.4 cm−1. The narrowness of this band makes it a good choice for investigating the influence of free rotation about the single C–C bond on the vibrational bands. Free internal rotation in ethylidyne on supported platinum at 77 K has been reported in an NMR study. We consider the vibration–rotation selection rules for an adsorbed molecule freely rotating about the surface normal. We show that the observable vibrational bands cannot exhibit rotational fine structure. However, nonsurface dipole allowed modes observable in transmission IR studies of supported metals are much too narrow to be consistent with free rotation of the CH3 group. The NMR and IR results are consistent if the exchange of the hydrogen atoms among three equivalent sites is fast on the NMR time scale but slow on the IR time scale.
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    The Journal of Chemical Physics 87 (1987), S. 5578-5579 
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    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: First results are presented on velocity distribution measurements of Ba+ ions drifted in helium using a well-characterized drift tube and single-frequency laser-induced fluorescence detection. Reduced mobilities of Ba+ in helium are obtained for E/N values between 7.74 and 23.2 Td. The velocity distributions that are observed parallel to the electric field fit a displaced Maxwell–Boltzmann distribution, in agreement with theoretical predictions. However, the temperatures parallel and perpendicular to the field are not in good agreement with theoretical treatments.
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    The Journal of Chemical Physics 87 (1987), S. 5562-5577 
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    Topics: Physics , Chemistry and Pharmacology
    Notes: We report the synthesis of the OH intermediate from O and H coadsorbed on the Rh(100) surface at 90 K and heated in ultrahigh vacuum (UHV) to between 140 and 240 K; the species is stable when cooled again to 90 K. When heated to higher than ≈240 K H2O is formed and evolved from the surface, demonstrating that OH formation is an important step in H2O synthesis. Temperature programmed electron energy loss spectroscopy (TP-EELS), temperature programmed reaction spectroscopy (TPRS), and low energy electron diffraction (LEED) were employed in the study of this intermediate. The EEL spectra of the OH species is characterized by a stretch mode at 394 meV, bending mode at 114 meV, frustrated lateral translation at 82 meV, and frustrated vertical translation at 54 meV. Off-specular measurements show that the OH bending mode is entirely dipole active at an impact energy of 6eV. By monitoring the OH bend intensity normalized to the elastic intensity as the crystal temperature is linearly ramped, the kinetics of both OH synthesis and OH combination to form H2O was probed. Kinetics was obtained using the heating rate variation method (from the shift in the temperature of fastest reaction Tp with heating rate) and the coverage variation method (from the shift in Tp resulting from different reactant concentrations). An activation energy of Ef=4±1 kcal mol−1 for OH formation was obtained. We find a half-order coverage dependence indicating that OH formation occurs at the perimeters of O islands. An activation energy of Ec=24±1 kcal/mol−1 was obtained for the combination reaction. Isotopic substitution of deuterium (D) for hydrogen yielded no OD or D2O under UHV conditions, but an O covered surface heated in a D2 pressure ≥10−8 Torr formed both surface OD and evolved D2O. This difference in H and D reactivity can be explained by the combination of the observed inverse kinetic isotope effect (KIE) in D2 recombinative desorption (in which D2 desorbs faster than H2) and the observed normal KIE in OD formation (in which OD forms at a slower rate than OH).
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