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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 110 (1999), S. 3876-3886 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new 11-electron relativistic effective core potential (11e-RECP) for Ag atom based on correlated level of theory and the associated atomic orbital (AO) basis set have been derived which allows for an accurate determination of excited states. This has been verified by comparing the calculated excited states of the dimer with experimental data. Therefore, we applied the new 11e-RECP in the framework of the linear response equation-of-motion coupled-cluster (EOM-CC) method to determine absorption spectra of small Agn=2−4 and Agn=2−4+ clusters. The correlation treatment of 11 electrons per atom and calculations of transition energies and oscillator strengths in a large energy interval allowed us to investigate the influence of d-electrons on the spectroscopic patterns. We have found that d-electrons play a crucial role for accurate predictions of absorption spectra in spite of the fact that they are not always directly involved in the leading excitations contributing to the intense transitions. The calculated spectroscopic patterns for the stable structures are compared with available experimental data. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 3431-3444 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We propose a semiclassical wave packet propagation method relying on classical trajectories in a complex phase space. It is based on the Schrödinger wave equation and the usual expansion with respect to (h-dash-bar), except that the amplitude of the wave packet is taken into account at the very zeroth order, unlike in the usual WKB method where it is treated as a corrective or first order term. Formally, it amounts to making both the wavelength and the width of the wave packet tend to zero with (h-dash-bar). The action and consequently the classical trajectories derived are complex. This method is tested successfully in many cases, analytically or numerically, including the bounce and even the splitting of the wave packet. Our method appears to be much more accurate than the WKB method while less computationally demanding than the Van-Vleck formula. Moreover, it has a particularly interesting property: the singularities (caustics) of the usual semiclassical theories do not appear in this formalism in all cases tested. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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