Efficient and Flexible Computation of Many-Electron Wave Function Overlaps

A new algorithm for the computation of the overlap between many-electron wave functions is described. This algorithm allows for the extensive use of recurring intermediates and thus provides high computational efficiency. Because of the general formalism employed, overlaps can be computed for varyin...

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Veröffentlicht in:Journal of chemical theory and computation Jg. 12; H. 3; S. 1207 - 1219
Hauptverfasser: Plasser, Felix, Ruckenbauer, Matthias, Mai, Sebastian, Oppel, Markus, Marquetand, Philipp, González, Leticia
Format: Journal Article
Sprache:Englisch
Veröffentlicht: United States American Chemical Society 08.03.2016
ISSN:1549-9618, 1549-9626
Online-Zugang:Volltext
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Zusammenfassung:A new algorithm for the computation of the overlap between many-electron wave functions is described. This algorithm allows for the extensive use of recurring intermediates and thus provides high computational efficiency. Because of the general formalism employed, overlaps can be computed for varying wave function types, molecular orbitals, basis sets, and molecular geometries. This paves the way for efficiently computing nonadiabatic interaction terms for dynamics simulations. In addition, other application areas can be envisaged, such as the comparison of wave functions constructed at different levels of theory. Aside from explaining the algorithm and evaluating the performance, a detailed analysis of the numerical stability of wave function overlaps is carried out, and strategies for overcoming potential severe pitfalls due to displaced atoms and truncated wave functions are presented.
Bibliographie:ObjectType-Article-1
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ISSN:1549-9618
1549-9626
DOI:10.1021/acs.jctc.5b01148