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Mixed-order semiclassical dynamics in coherent state representation: The connection between phonon sidebands and guesthost dynamics
 

Summary: Mixed-order semiclassical dynamics in coherent state representation:
The connection between phonon sidebands and guest­host dynamics
M. Ovchinnikov and V. A. Apkarian
Department of Chemistry, University of California, Irvine, California 92697-2025
Received 3 September 1997; accepted 29 October 1997
The formalism of mixed-order semiclassical molecular dynamics in coherent state representation is
developed and applied to calculations of quantum time correlation functions in extended systems.
The method allows the consistent treatment of a selected number of degrees of freedom to second
order in the stationary phase approximation, through the Herman and Kluk propagator, while the
rest of the system is treated to zeroth order, using frozen Gaussians. The formulation is applied to
calculate the absorption spectrum, of the BX transition of Cl2 isolated in solid Ar a spectrum that
shows zero-phonon lines and phonon sidebands with relative intensities that depend on the excited
state vibrational level. The explicit simulation of quantum time correlation functions of the system
consisting of 321 degrees of freedom, reproduces the spectrum and allows its interpretation in terms
of the underlying molecular motions. Details of the dynamics of a chromophore coupled to lattice
phonons are discussed. © 1998 American Institute of Physics. S0021-9606 98 50106-7
I. INTRODUCTION
That spectral observables in condensed media are most
naturally treated in terms of time-dependent quantum corre-
lation functions is well recognized. In systems of large di-

  

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

 

Collections: Chemistry