Implementation of a fast analytic ground state potential energy surface for the N(2D)+H2 reaction

A new implementation is presented for the potential energy surface (PES) of the 1 (2)A() state of the N(D-2)+H-2 system based on a set of 2715 ab initio points resulting from the multireference configuration interaction (MRCI) calculations. The implementation is carried out using the reproducing Kernel Hilbert Space interpolation method. Range parameters, via bond-order-like coordinates, are properly chosen to render a sufficiently short-range three-body interaction and a regularization procedure is invoked to yield a globally smooth PES. A fast algorithm, with the help of low-order spline reproducing kernels, is implemented for the computation of the PES and, particularly, its gradients, whose fast evaluation is essential for large scale quasi-classical trajectory calculations. It is found that the new PES can be evaluated more than ten times faster than that of an existing (old) PES based on a smaller number (1141) of data points resulting from the same MRCI calculations and a similar interpolation procedure. Although there is a general good correspondence between the two surfaces, the new PES is in much better agreement with the ab initio calculations, especially in key stationary point regions including the C-2v minimum, the C-2v transition state, and the N-H-H linear barrier. Moreover, the new PES is free of spurious small scale features. Analytic gradients are made available in the new PES code to further facilitate quasiclassical trajectory calculations, which have been performed and compared with the results based on the old surface. (C) 2003 American Institute of Physics.