A linear algebraic method for exact computation of the coefficients of the 1/ D expansion of the Schrödinger equation

• Published in: The Journal of chemical physics 1994-10, Vol.101 (7), p.5987-6004
• Main Authors: Dunn, Martin, Germann, Timothy C., Goodson, David Z., Traynor, Carol A., Morgan, John D., Watson, Deborah K., Herschbach, Dudley R.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.467314

The 1/D expansion, where D is the dimensionality of space, offers a promising new approach for obtaining highly accurate solutions to the Schrödinger equation for atoms and molecules. The method typically employs an asymptotic expansion calculated to rather large order. Computation of the expansion coefficients has been feasible for very small systems, but extending the existing computational techniques to systems with more than three degrees of freedom has proved difficult. We present a new algorithm that greatly facilitates this computation. It yields exact values for expansion coefficients, with less roundoff error than the best alternative method. Our algorithm is formulated completely in terms of tensor arithmetic, which makes it easier to extend to systems with more than three degrees of freedom and to excited states, simplifies the development of computer codes, simplifies memory management, and makes it well suited for implementation on parallel computer architectures. We formulate the algorithm for the calculation of energy eigenvalues, wave functions, and expectation values for an arbitrary many-body system and give estimates of storage and computational costs.