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  • Elsevier  (1,387)
  • American Association for the Advancement of Science  (68)
  • American Institute of Physics (AIP)  (64)
  • Amsterdam : Elsevier
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  • 11
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 250-261 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: NH stretching overtone and combination states in HN3 X˜ 1A' were excited by IR–visible double resonance pumping and by direct overtone pumping in the range 6ν1 (17 670 cm−1) to 7ν1 (20 070 cm−1). NH fragments in the a 1Δ and X 3Σ− states were detected by laser induced fluorescence with sub-Doppler resolution to determine branching ratios, correlated fragment rotational state and kinetic energy distributions, and fragment vector correlations. The spin-forbidden triplet channel was accessible to all states excited, while the threshold for the singlet channel was determined to lie in the range 18 190 to 18 755 cm−1. The measured energy release places limits on the HN–NN bond energy, and the heights of barriers to reaction. The barrier in the singlet exit channel is at least 540 cm−1. The singlet channel accessed by 7ν1 dissociation is characterized by a Boltzmann-like NH rotational distribution (〈J NH〉≈3.5), highly excited N2 rotations (〈JN2〉 ≥ 20), and total translational energy release peaked away from zero (〈ET〉≈1350 cm−1). Vector correlations and Λ-doublet propensities indicate that nonplanar dissociation processes influence the NH rotations, but become less important for higher NH rotational states. The principal correlations are a strong positive recoil anisotropy (β≈0.6), a weak positive v–J correlation (βvJ≈0.17), and a JNH-dependent Λ-doublet propensity. A model using parent vibrational motion projected onto fragment rotation is suggested to explain these observations. The triplet channel exhibits similar NH and N2 rotational state distributions, with most of the available energy (substantially greater than in the singlet channel) appearing as fragment kinetic energy.
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  • 12
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 2782-2789 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High-resolution spectra have been obtained for the predissociative N–H stretching overtone levels 5ν1 (15 120 cm−1) and 6ν1 (17 670 cm−1) of HN3, cooled in a free-jet expansion. The spectral bandwidth (Doppler limited at 0.007 cm−1 full width at half-maximum (FWHM) is sufficiently narrow to reveal the homogeneous linewidths of individual rovibrational transitions in the 6ν1 band, for which we previously measured the dissociation lifetime in time-domain experiments. Two distinct manifestations of vibrational coupling characterize the spectra: (a) anharmonic mixing of the N–H stretch with other vibrational motions to give a complex spectrum of vibrational eigenstates and (b) homogeneous widths of the resultant states determined by the dissociation lifetime. The results are discussed with reference to previous studies of overtone spectroscopy and intramolecular mixing. Time-domain measurements of dissociation rates are reported for four vibrational levels with zero-order labels 5ν1 +νx. Over the range 15 100 cm−1–17 700 cm−1, the dissociation rate increases monotonically with vibrational energy, with no apparent "mode-specific'' variations. This is interpreted in terms of the highly mixed character of any particular vibrational eigenstate that is excited.
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  • 13
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 608-609 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Excitation of the NH-stretch overtone transitions of HN3 to v1=5 and 6 resulted in predissociation to HN(X) and N2(X) with lifetimes of 80+60−30 and ≤3 ns, respectively. Following excitation of either overtone, the HN fragments were formed predominantly in the symmetric F1, F3 spin–rotation states, with less than 4% population in the antisymmetric F2 levels. Fragment Doppler profiles confirmed that most of the available energy (〉96%) went into translational motion.
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  • 14
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 6262-6275 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The IBr fragment rotational state distributions that result when the NeIBr van der Waals molecule undergoes vibrational predissociation have been measured in a pump–probe laser-induced fluorescence experiment. Independent of initial vibrational state and the number of quanta of vibrational energy lost from the I–Br coordinate, the rotational distributions extend over the full range of energetically accessible states. From the observation of energetic constraints on the rotational distribution, the dissociation energy (D0) is calculated to be 65.5±1.2 cm−1 for the A electronic state, v=16. For the X electronic state, v=0, D0=71.8±1.2 cm−1. Quantum mechanical bound state calculations carried out on a model A electronic state potential energy surface are in quantitative agreement with this result. The rotational distributions are broader than that predicted by either a Franck–Condon or classical impulsive model for the dissociation. The distributions are qualitatively in accord with classical trajectory calculations. Analysis of specific rotational distributions in the context of the energy gap law shows poor quantitative agreement. The average fragment rotational energy relative to analogous Ne-containing complexes is, however, qualitatively predicted by the energy gap relations.
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  • 15
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 4619-4620 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The vibrational relaxation dynamics of CO chemisorbed on small Pt and Rh particles supported on SiO2 has been investigated by picosecond time-resolved infrared transient bleaching experiments. A vibrational T1 lifetime of ≈7 ps has been observed for several different samples, independent of polarization, pump intensity, and sample temperature from 100–400 K. A 1:3 isotopic dilution has no effect upon T1. This T1 lifetime is a factor of 10–50 times shorter than T1 reported for metal carbonyl cluster compounds in solution and on SiO2 supports. Two possible mechanisms are considered to account for the rapid T1 decay; redistribution of the energy throughout the broad CO vibrational band, and relaxation directly to electron–hole pairs in the metal particles.
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  • 16
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 3171-3180 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The A 3Π1←X 1Σ+ laser-induced fluorescence excitation spectrum of the NeIBr van der Waals complex is reported and analyzed to extract information regarding the structure and vibrational predissociation dynamics of the complex. While no definitive geometric information regarding NeIBr is obtained, our data indicate that a linear geometry is at least plausible. The vibrational predissociation lifetimes are a strong function of A state vibrational level and range from 2.6 to 23 ps. The variation in lifetime with vibrational level is consistent with the results of previous measurements on rare gas–halogen complexes, particularly NeBr2.
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  • 17
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5342-5343 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Infrared pump–probe characterization of the excited state lifetimes reveals that CO bound to isolated metal sites (T1=140±20 ps) persists longer than the signal observed for CO bound to (approximate)35 A(ring) diameter metal particles (≤18 ps), suggesting paticipation of electron–hole excitations in the larger metal particles.
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  • 18
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 230-239 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Tunable infrared picosecond pulses in the 5 μ region have been used for time-resolved pump–probe measurements of the population relaxation lifetime (T1) of CO(v=1) stretching vibrations in a series of metal–carbonyl cluster compounds in room temperature chloroform solution. T1 was the same for symmetric (ν=2084 cm−1, 90±10 ps) and antisymmetric (2014 cm−1, 87±10 ps) modes of the dicarbonyl Rh(CO)2(C5H7O2); T1 was the same for the B1 (2092 cm−1 , 710±130 ps) and B2 (2036 cm−1, 750±90 ps) modes of Rh2(CO)4Cl2. Similarly long T1 times were found for Rh4(CO)12 (2075 cm−1, 610±65 ps) and Rh6(CO)16 (2077 cm−1, 700±100 ps). The molecule Co4(CO)12 has also been compared to the corresponding rhodium analog and it exhibits an initially fast relaxation of 47±5 ps followed by a slower 396±70 ps decay. The transient response of the more complex systems to the single frequency experiment is found to be sensitive to frequency and can exhibit bleaching, absorption, and a combination of these effects. Such behavior is attributed to overlap of the IR pulse with v=1 to v=2 and higher transitions in the M4(CO)12 (M=Rh or Co) and Rh6(CO)16 molecules. The long CO(v=1) T1 values for the metal cluster molecules suggest relaxation via multiquantum transfer of vibrational energy to adjacent M–C stretch and M–C–O bend vibrations; energy transfer to vibrational or electronic states of the central metal core seems unimportant in determining T1 for these systems.
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  • 19
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3536-3541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The degree of vibrational excitation in the IBr fragment from the vibrational predissociation of NeIBr (A 3Π1) has been measured using two-color pump–probe laser-induced fluorescence spectroscopy. We find that for the lowest initial vibrational states examined, Δv=−1 dissociation pathways dominate the dynamics, while this channel is closed for v≥17. From this result, the A state binding energy (D0) of the complex is determined to be 67±4 cm−1, while that in the X electronic state is found to be 73±4 cm−1. The X state binding energy is identical to that for NeI2 and NeBr2, suggesting that the potential energy surface for NeIBr can be constructed from a summation of atom–atom pair potentials; we present such a model potential energy surface. The variations in the vibrational branching ratios, when combined with the trends in the predissociation rates, point to the importance of fragment rotational excitation in the dynamics of the dissociation.
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  • 20
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 7037-7045 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrational overtone photodissociation is used to examine the spectroscopy and vibrational predissociation lifetimes of HN3 in its ground electronic state. Direct overtone pumping of the N–H stretching levels 5νNH and 6νNH prepares molecules in selected states (v,J,K) near 15 100 and 17 700 cm−1 of vibrational energy; spin-forbidden NH(X 3 Σ−) dissociation fragments are detected by laser-induced fluorescence. Photodissociation spectra of beam-cooled HN3 display mixing of individual rotational levels of the nνNH vibrations with several background states, with derived coupling matrix elements in the range 0.01–0.1 cm−1. Vibrational predissociation lifetimes of mixed components of 5νNH are state specific, with variations of a factor of 2 for only 0.1 cm−1 energy differences. Average lifetimes for low J, K are 210 ns for 5νNH and 0.95 ns for 6νNH. The ratio of decay rates for the two overtone levels, k(6νNH)/k(5νNH)=220, is much greater than predicted by statistical theory, which gives a ratio of 4.
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