ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
An efficient procedure based on the reproducing kernel Hilbert space interpolation method is presented for constructing intermolecular potential energy surfaces (PES) using not only calculated ab initio data but also a priori information on long-range interactions. Explicitly, use of the reciprocal power reproducing kernel on the semiinfinite interval [0,∞) yields a set of exact linear relations between dispersion (multipolar) coefficients and PES data points at finite internuclear separations. Consequently, given a combined set of ab initio data and the values of dispersion (multipolar) coefficients, the potential interpolation problem subject to long-range interaction constraints can be solved to render globally smooth, asymptotically accurate ab initio potential energy surfaces. Very good results have been obtained for the one-dimensional He–He potential curve and the two-dimensional Ne–CO PES. The construction of the Ne–CO PES was facilitated by invoking a new reproducing kernel for the angular coordinate based on the optimally stable and shape-preserving Bernstein basis functions. © 2000 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1288268
