INVERSE PERTURBATION VIA SINGULAR-VALUE DECOMPOSITION - APPLICATION TO CORRECTION OF POTENTIAL SURFACE FOR HCN

Citation
Q. Wu et al., INVERSE PERTURBATION VIA SINGULAR-VALUE DECOMPOSITION - APPLICATION TO CORRECTION OF POTENTIAL SURFACE FOR HCN, The Journal of chemical physics, 107(9), 1997, pp. 3602-3610
Citations number
20
Categorie Soggetti
Physics, Atomic, Molecular & Chemical
ISSN journal
00219606
Volume
107
Issue
9
Year of publication
1997
Pages
3602 - 3610
Database
ISI
SICI code
0021-9606(1997)107:9<3602:IPVSD->2.0.ZU;2-6
Abstract
We report a new potential energy surface (PES) for HCN which is able t o exactly reproduce experimentally measured eigenvalues for total angu lar momentum of J=0 and 1. The new PES is obtained by adding a correct ion Delta V to a previous PES of Bowman et al., and the correction Del ta V is determined through a direct inversion technique based on first -order inverse perturbation via singular value decomposition as descri bed in a previous publication. Since the PES of Bowman et al. is a goo d starting PES, the inversion calculation is relatively straightforwar d. A total of 51 and 20 experimental eigenvalues, respectively, for J= 0 and J=K=1, including both the H-CN and H-NC configurations, are used in the inversion calculation. Absolutely accurate eigenvalues (maximu m deviation of less than 0.01 cm(-1) from experimental values) on the new PES cm obtained. Since the potential correction Delta V is express ed in a basis set, the corrected new PES is an analytical function of the coordinates. The contours of the new PES and of the potential corr ection Delta V are plotted to show locations of the correction to the PES of Bowman et al. (C) 1997 American Institute of Physics.