Nonproduct quadrature grids for solving the vibrational Schrödinger equation.
The size of the quadrature grid required to compute potential matrix elements impedes solution of the vibrational Schrodinger equation if the potential does not have a simple form. This quadrature grid-size problem can make computing (ro)vibrational spectra impossible even if the size of the basis used to construct the Hamiltonian matrix is itself manageable. Potential matrix elements are typically computed with a direct product Gauss quadrature whose grid size scales as N(D), where N is the number of points per coordinate and D is the number of dimensions. In this article we demonstrate that this problem can be mitigated by using a pruned basis set and a nonproduct Smolyak grid. The constituent 1D quadratures are designed for the weight functions important for vibrational calculations. For the SF(6) stretch problem (D=6) we obtain accurate results with a grid that is more than two orders of magnitude smaller than the direct product Gauss grid. If D>6 we expect an even bigger reduction.
Avila
Gustavo
G
Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada. gustavo_avila@telefonica.net
Carrington
Tucker
T