Accurate and highly efficient calculation of the highly excited pure OH stretching resonances of O(D-1)HCl, using a combination of methods

摘要

Accurate calculation of the energies and widths of the resonances of HOCl-an important intermediate in the O(D-1)HCl reactive system-poses a challenging benchmark for computational methods. The need for very large direct product basis sets, combined with an extremely high density of states, results in difficult convergence for iterative methods. A recent calculation of the highly excited OH stretch mode resonances using the filter diagonalization method, for example, required 462000 basis functions, and 180000 iterations. In contrast, using a combination of new methods, we are able to compute the same resonance states to higher accuracy with a basis less than half the size, using only a few hundred iterations-although the CPU cost per iteration is substantially greater. Similar performance enhancements are observed for calculations of the high-lying bound states, as reported in a previous paper [J. Theo. Comput. Chem. 2, 583 (2003)]. (C) 2004 American Institute of Physics.