Abstract
In this paper we propose a scheme for choosing basis functions for quantum dynamics calculations. Direct product bases are frequently used. The number of direct product functions required to converge a spectrum, compute a rate constant, etc., is so large that direct product calculations are impossible for molecules or reacting systems with more than four atoms. It is common to extract a smaller working basis from a huge direct product basis by removing some of the product functions. We advocate a build and prune strategy of this type. the one-dimensional (1D) functions from which we build the direct product basis are chosen to satisfy two conditions: (1) they nearly diagonalize the full Hamiltonian matrix; (2) they minimize off-diagonal matrix elements that couple basis functions with diagonal elements close to those of the energy levels we wish to compute. by imposing these conditions we increase the number of product functions that can be removed from the multidimensional basis without degrading the accuracy of computed energy levels. Two basic types of 1D basis functions are in common use: eigenfunctions of 1D Hamiltonians and discrete variable representation (DVR) functions. Both have advantages and disadvantages. the 1D functions we propose are intermediate between the 1D eigenfunction functions and the DVR functions. If the coupling is very weak, they are very nearly 1D eigenfunction functions. as the strength of the coupling is increased they resemble more closely DVR functions. We assess the usefulness of our basis by applying it to model 6D, 8D, and 16D Hamiltonians with various coupling strengths. We find approximately linear scaling.
Recommended Citation
R. Dawes and T. Carrington, "How to Choose One-Dimensional Basis Functions So That a Very Efficient Multidimensional Basis May Be Extracted From a Direct Product of the One-dimensional Functions: Energy Levels of Coupled Systems with as Many as 16 Coordinates," Journal of Chemical Physics, vol. 122, American Institute of Physics (AIP), Apr 2005.
The definitive version is available at https://doi.org/10.1063/1.1863935
Department(s)
Chemistry
Keywords and Phrases
Coupling strengths; Discrete variable representation (DVR); One-dimensional basis functions; Prune strategy; Atoms; Diagnosis; Eigenvalues and eigenfunctions; Extraction; Hamiltonians; Matrix algebra; Electron energy levels
International Standard Serial Number (ISSN)
0021-9606
Document Type
Article - Journal
Document Version
Final Version
File Type
text
Language(s)
English
Rights
© 2005, American Institute of Physics (AIP), All rights reserved.
Publication Date
01 Apr 2005
