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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 2629-2634 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photoelectron spectra of the weakly bound KrO− anion are simulated using a theory which combines the atoms-in-molecule model for molecular electronic wave functions and the Rau–Fano model for photodetachment intensities [J. Chem. Phys. 112, 5852 (2000)]. The nonrelativistic potential energy curves of the anion are obtained from ab initio calculations. The calculated spectra and their temperature variation agree with the experimental data presented in the preceding article. The strong selectivity of the photodetachment process with respect to the symmetry of fine-structure components is rationalized and quantified. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 5852-5865 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A combined ab initio atoms-in-molecule approach was implemented to model the photoelectron spectra of the ArO− anion. The lowest adiabatic states of Σ and Π symmetry of ArO and ArO− were investigated using the fourth-order Møller–Plessett perturbation theory including bond functions. The total energies were dissected into electrostatic, exchange, induction, and dispersion components. The complex of Ar with atomic oxygen is only weakly bound, primarily by dispersion interaction. The Π state possesses a deeper minimum (Re=3.4 Å,De=380 μEh) than the Σ state (Re=3.8 Å,De=220 μEh). In contrast, the anion complex is fairly strongly bound, primarily by ion-induced dipole induction forces, and the Σ state possesses a deeper minimum at shorter interatomic distances (Re=3.02 Å,De=3600 μEh) than the Π state (Re=3.35 Å,De=2400 μEh). The Σ–Π splittings in both systems are mainly due to differences in the exchange repulsion terms. Atoms-in-molecule models were used to account for the spin–orbit interaction, and to generate adiabatic relativistic potentials and wave functions. Collisional properties, diffusion, and mobility coefficients of O and O− in Ar, and absolute total Ar+O scattering cross sections, were calculated and found to agree well with the available experimental data. The photoelectron spectra were simulated within vibronic model, and were found in excellent agreement with the experimental measurements. The bimodal electron kinetic energy distribution was shown to stem from the strong selectivity of spin–orbit transitions, which split into two dense groups, depending on the initial electronic state of the anion. The latter feature cannot be described without explicit consideration of electronic intensity factor. © 2000 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 111 (1999), S. 2470-2477 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrational predissociation dynamics of ArHF and ArDF complexes is investigated theoretically for the first time owing to the use of three-dimensional potential energy surfaces (PES's) based on the diatomics-in-molecule approach [J. Chem. Phys. 104, 5510 (1996)]. The original PES is improved empirically to yield a reasonable description of the lowest vibrational energy levels of the ArHF complex at J=0. Predissociation dynamics is studied by means of line shape and diabatic Fermi Golden Rule methods. The latter is found to provide excellent results for the total decay widths but only a qualitative estimate for the product rotational distributions. It is shown that predissociation dynamics is governed by vibrational to rotational energy transfer. The decay proceeds almost entirely into the highest accessible rotational product channel. This propensity manifests itself in the decrease of the predissociation lifetime upon increasing vibrational excitation of the diatomic fragment when the highest rotational channel appears to be closed. Another source of state specificity in the vibrational predissociation is the anisotropy of the PES. Absolute calculated lifetime values are likely too small, but exhibit some qualitative trends observed experimentally. © 1999 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 6282-6290 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Extensive classical investigation of the vibrational predissociation dynamics of the model He(centered ellipsis)Br2 and Rg(centered ellipsis)I2 (Rg=He, Ne, and Ar) van der Waals complexes is performed. Classical trajectory calculations of the fragmentation rates are accomplished with the numerical analysis of the phase-space structure within the two-dimensional T-shaped model. Various bifurcations of the phase portrait with increasing excitation energy are found to produce a remarkable effect on the fragmentation dynamics causing irregular variations of the decay rate. This effect is proven to be quite persistent and pertinent to the more realistic three-dimensional dynamics as well. The implications of the results for studying quantum-classical correspondence for metastable states are indicated. © 1998 American Institute of Physics.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 4358-4358 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 9913-9925 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Semiempirical model is developed for studying the electronic structure of the rare gas atom–halogen molecule systems. It is formulated in the frame of diatomics-in-molecule (DIM) approach and takes explicitly into account strong spin–orbit coupling pertinent to heavy halogen molecules. The consistent DIM scheme is realized for intermolecular interactions, whereas the description of valence electronic states of halogen molecule is more approximate being based on the asymptotic wave functions. The corresponding perturbation theory is also put forward. The model is applied to analysis of several features of the Ar...I2 van der Waals complex. First, the calculations on the spectroscopic constants of the B←X transition in the complex reveal the quantitative performance of the model. Second, mechanisms of nonadiabatic dynamics are examined. The results are qualitatively consistent with the current view on the Ar...I2 electronic predissociation and one-atom cage effect. Third, the prediction is made on the valence electronic spectrum of Ar...I2 complex. These examples demonstrate the reliability of the model. © 1996 American Institute of Physics.
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  • 7
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: First-order perturbative approximations to the diatomics-in-molecule (DIM) approach are implemented for studying interactions between the neon atom and chlorine molecule in the X 1Σg+(0+) and B 3Πu(0+) states. Intermolecular DIM perturbation theory (IDIM PT1) [J. Chem. Phys. 104, 9913 (1996)], which accounts for the atomic component of spin-orbit interaction, is compared to the anisotropic model by Naumkin and Knowles [J. Chem. Phys. 103, 3392 (1995)] which is proven to be a first-order approximation to the nonrelativistic DIM approach. An importance of the spin-orbit effects for the ground-state potential energy surface (PES) is demonstrated. Semiempirical PESs are used in the accurate quantum calculations on the vibrationally averaged geometry, B←X vibronic spectra, and vibrational predissociation dynamics of the Ne(centered ellipsis)Cl2 van der Waals complex. The IDIM PT1 model is shown to provide good agreement with available experimental data. The effects of interaction potential topology on the spectroscopic and dynamic properties of the complex and the relation of DIM-based PESs to the results of ab initio calculations are discussed. © 1997 American Institute of Physics.
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  • 8
    ISSN: 0192-8651
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Vibrational and rotational decoupling approximations are tested in three-dimensional Fermi Golden Rule calculations on energies, lifetimes, and product state distributions of the vibrationally predissociating atom - diatom van der Waals complexes. The validity of approximate separations of diatom vibration, decoupling of stretching and bending intermolecular motions, and rotational infinite order sudden approximation for product scattering is characterized by comparison with the results of accurate calculations on the Ne ··· Cl2, Ne ··· ICl, and He ··· ICl systems. The most accurate approximate schemes are recommended. © 1996 by John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1573-8779
    Source: Springer Online Journal Archives 1860-2000
    Topics: 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 98 (1993), S. 5486-5498 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Approximate version of the phase-space transport theory for vibrational predissociation of the van der Waals complexes with two degrees of freedom is proposed and tested. The theory uses the concept of phase-space bottlenecks which govern the phase-point stochastic diffusion. The global transport is treated as a sequence of the transitions across the bottlenecks within a kineticlike model. Simplified formulas for the transition probabilities across dissociation separatrix (intermolecular bottleneck) and Golden cantori (intramolecular bottlenecks) are obtained under the zeroth-order approximation. Applications to some model complexes indicate the ability of the model to reproduce correctly individual bottleneck parameters as well as the total predissociation rates. Some observations concerning the multibottleneck kinetic models are discussed.
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