A new quasiclassical method for modeling the high-resolution spectra of polyatomic systems.
A new quasiclassical method for quantum autocorrelation functions based on the semiclassical limit in Wigner phase space has been derived. Unlike the existing quasiclassical method, the new method enables long-time simulations, thus making it possible to locate quantum spectral lines very precisely. The new method has been tested for a one-dimensional anharmonic oscillator fitted to the H(2) molecule and for a six-dimensional calculation of the Ar(2)I van der Waals cluster in adiabatic approximation. The obtained results compare well with the benchmark quantum-mechanical calculations and are also roughly comparable to the experimental Ar(2)I(-) zero-kinetic-energy photoelectron spectrum, which is available in the literature.
Kaprálová-Zd'ánská
Petra R
PR
J Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague 8, Czech Republic. petra.kapralova@jh-inst.cas.cz
Hanák
Filip
F
Lazebnícek
Jan
J