WIGNER DVR: A NEW METHOD FOR THE CALCULATION OF VRT DYNAMICS OF VAN DER WAALS CLUSTERS
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Date
1995
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
Given the existence of a large body of precise spectroscopic data for weakly bound $complexes^{1}$, the determination of multidimensional intermolecular potential energy surfaces (IPS's) has been limited by available computer technology and computational techniques. Due to these limitations, the most complex IPS that has been fitted to date is that for the 4-D $(HCl)_{2}.^{2}$ New dynamics methods have recently been developed for the efficient evaluation of the hamiltonian using a Wigner $DVR^{3}$ (discrete variable representation). This new technique has been applied to the 4-D $(HCl)_{2}$ and was combined with the complementary Lanczos algorithm for efficient diagonalization of the resulting matrix. The accuracy is comparable to that of the variational technique. The time requirements of these new methods were compared with those of Elrod and Saykally for the $(HCl)_{2}$ and found to be reduced by more than half., whereas, memory limitations were virtually eliminated. Following these encouraging results, these methods are being applied to the 6-D $(HF)_{2}$.
Description
$^{1}$R. J. Saykally and G. A. Blake, Science, 1993, 259, 1570-1575 $^{2}$M.J. Elrod and R.J. Saykally, in press, Journal of Chemical Physics $^{1}$C. LeForestier, JCP, 1994, 101, 7357-7363
Author Institution: University of California, Berkeley, CA 94720; Universite Paris-Sud, Batiment 490, 91405 Orsay, France.
Author Institution: University of California, Berkeley, CA 94720; Universite Paris-Sud, Batiment 490, 91405 Orsay, France.