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
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.