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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 7808-7812 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio Hartree–Fock (HF) and second-order many-body perturbation theory (E2) were used to generate data for pair potentials of the mixtures CH4–H2S and CH4–H2O. The points were fit with site–site functions consisting of terms for interactions of the following types: exponential repulsion and R−6 and electrostatic attraction. The basis sets of Gaussian functions were developed by systematically adding polarization functions to maximize the zeroth-order dipole polarizability; the counterpoise method was used to correct basis set superposition error. The best well depths calculated for CH4–H2S and CH4–H2O were −0.0227 and −0.0215 eV, respectively (with no experimental results available for comparison). The potentials were evaluated by examining errors in the dipole polarizabilities and pressure second virial coefficients.
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 7068-7078 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution stimulated Raman spectroscopy (SRS) has been used to examine N2 and N2/He free jet expansions and also equilibrium samples of N2 from 15 to 110 K. The jet spectra show the formation of large liquid clusters which supercool and subsequently freeze to form crystalline β-N2 solid and, in He expansions, undergo a further transformation to a partially annealed α-N2 form. CW-SRS frequency and linewidth data obtained for equilibrium samples of the condensed phases of N2 yielded frequency–temperature relations used in deducing internal temperatures for the clusters produced in the expansion experiments. Analysis of the cooling curves indicates a mean cluster diameter of 35 nm and favors a prompt freezing process rather than a gradual conversion of liquid to solid in a single cluster on the microsecond time scale of the experiments. Supercooling limits of 34 to 44 K are deduced for the liquid, far below the triple point temperature of 63.2 K at which equilibrium samples freeze. Some evidence for surface versus bulk contributions to the spectra is seen in the asymmetric line shapes observed for liquid clusters in the condensation region. The results show that the high spectral and spatial resolution of nonlinear Raman methods such as SRS and CARS provide a unique probe of the condensation processes in free jet expansions.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5560-5567 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The acoustic waves generated by a relaxing gas have a shape which depends on the ratio of the relaxation rate to the acoustic propagation rate. It is shown how the relaxation time constant can be extracted from this waveform for a variety of relaxation rate laws, using a Green's function to solve the linearized wave equation. The accuracy of the method is confirmed by measuring the relaxation rate constants for OCS diluted in Ar and He. These, plus a previous measurement of the relaxation rates of highly excited SF6 and C6F5H in Ar, are in good agreement with the literature.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 6306-6312 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We report observation of a reaction between a metal atom and silicon in a supersonic jet to form metal atom–silicon clusters. Using the technique of laser vaporization supersonic expansion with metal carbonyl seeded carrier gas, clusters of the form MSin have been detected by ArF and F2 laser photoionization time-of-flight mass spectrometry. Three group-VIB transition metals and copper have been investigated. The dominant product cluster peaks observed in the mass spectra obtained for all three group VIB metals corresponds to identical but remarkable cluster stoichiometries. The dominant product peaks have formulas given by MSin where n=16. Copper results are different than the other three metals, indicating the importance of the metal valence electronic structure to the chemistry. The metal–semiconductor clusters are relatively more stable towards photofragmentation than the bare silicon cluster of the same size. The observation of these new species may be relevant to reactions which occur at the interface between a silicon wafer and deposited metals.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 1681-1694 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Grassberger–Procaccia method has been employed to study the transitions which occur as a classical Ar3 cluster, modeled by pairwise Lennard-Jones potentials, passes from a rigid, solid-like form to a nonrigid, liquid-like form with increasing energy. Power spectra and lower bounds on the fractal dimensions and K entropies are presented at several energies along the caloric curve for the Ar3 cluster. In addition, the full spectrum of Liapunov exponents has been computed at these same energies to get an accurate value of the K entropy. Chaotic behavior, though relatively small, is observed even at low energies where the power spectrum displays largely normal-mode structure. The degree of chaotic behavior increases with energy at energies where some degree of regularity is observed in the spectrum. However, at energies that just allow the system to pass into and across saddle regions separating local potential minima, the phase space appears to be separable into a region within the equilateral triangle potential well where the behavior is highly chaotic, and a region of lower dimensions and less chaos around the saddle of the linear configuration. Dimensions from approximately three to eight are observed. A clear separability of time scales for establishment of different extents of ergodicity permits the determination of fractal dimensions of the manifold on which the phase points moves, for time scales of physical, i.e., observable significance. We believe this to be the first evaluation of the dimensionality of the space on which the phase point moves, for a Hamiltonian system displaying this range of dimensions.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 7981-7990 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In K–C2H2 collisions at collision energies 0.4(approximately-less-than)E(approximately-less-than)1.3 eV and scattering angles 40°(approximately-less-than)cursive-theta(approximately-less-than)180° surprisingly little transfer of energy from translation into the internal degrees of freedom of the acetylene molecule is found. The observations are consistent with the assumptions of electronically covalent encounters, insignificant activation of the acetylene vibrations, and rotational excitation produced by spindle-shaped equipotentials, nearly spherical in a broad vicinity of the C 3/4 C bond.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 1347-1357 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Classical dynamical studies are presented of melting and diffusive behavior in the Ar13 cluster. A comparison is made between the standard Einstein form for the diffusion constant (and the equivalent Green–Kubo form) and a recently developed theory for dynamics and diffusion in liquids based on the dynamical Hessian matrix. Comparisons are also made to similar calculations on melting in bulk argon systems. In the molecular dynamics calculations, it is found that the onset of liquidlike behavior occurs rather suddenly across the transition region. Well-defined Fick's Law diffusive behavior occurs in liquidlike clusters over time scales long relative to the characteristic vibrational period. In studies involving the dynamical matrix, the distributions and numbers of positive and negative eigenvalues of the Hessian matrix are monitored as a function of energy and temperature, and the Einstein frequency of the cluster is computed.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 3605-3609 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ab initio Hartree–Fock (HF) and many-body perturbation theory through second (E2) and third order (E3) were used to generate pair potentials for (H2S)2. Several basis sets were developed by optimizing polarization functions with the zeroth-order dipole or quadrupole polarizabilities. Approximately 30 ab initio points (fully counterpoised HF+E2) in each of two larger basis sets were fit with site–site potentials. Intermediate potentials for fewer points indicate that only about 30 points are a sufficient data base to predict energies in the vicinity of the well with an accuracy of about 10%. The best ab initio well depth produced (−0.0693 eV) lies at 94% of the only published experimental value (−0.074±0.013 eV), although arguments are presented which indicate that the true (H2S)2 minimum may lie below −0.08 eV. The role of E3 and nonadditive effects has also been explored, but they were found not to account for the major part of the remaining discrepancy between our best number and experiment.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 6338-6338 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5753-5763 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a numerically exact procedure for the calculation of an important class of finite temperature quantum mechanical time correlation functions. The present approach is based around the stationary phase Monte Carlo (SPMC) method, a general mathematical tool for the calculation of high dimensional averages of oscillatory integrands. In the present context the method makes possible the direct numerical path integral calculation of real-time quantum dynamical quantities for times appreciably greater than the thermal time (β(h-dash-bar)). Illustrative applications involving finite temperature anharmonic motion are presented. Issues of importance with respect to future applications are identified and discussed.
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