A method to reduce the size of the vibronic basis employed in the simulation of spectra using the multimode vibronic coupling approximation.
In the time-independent multimode approach for the determination of vibronic spectra involving strongly coupled electronic states, the equilibrium geometry and normal modes of the reference or precursor state are usually employed as the basis for the multimode expansion. This basis, while easily constructed, is generally ill-suited for determining the eigenstates of the observed species. Employing a more computationally effective basis requires the evaluation of Franck-Condon overlap integrals. Using established generalized Hermite polynomial generating function formalisms, an algorithm is developed that can efficiently determine the enormous requisite number of these overlap integrals. It is found that this flexibility in the choice of multimode basis can significantly reduce the size of the basis needed to obtain converged spectral simulations. The previously reported spectrum of the ethoxy (C(2)H(5)O) radical serves as an example of the efficacy of the new technique.
Schuurman
Michael S
MS
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Yarkony
David R
DR