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Title: Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps

Abstract

A simple and powerful method for comparing many-electron wavefunctions constructed at different levels of theory is presented. By using wavefunction overlaps, it is possible to analyze the effects of varying wavefunction models, molecular orbitals, and one-electron basis sets. The computation of wavefunction overlaps eliminates the inherent ambiguity connected to more rudimentary wavefunction analysis protocols, such as visualization of orbitals or comparing selected physical observables. Instead, wavefunction overlaps allow processing the many-electron wavefunctions in their full inherent complexity. The presented method is particularly effective for excited state calculations as it allows for automatic monitoring of changes in the ordering of the excited states. A numerical demonstration based on multireference computations of two test systems, the selenoacrolein molecule and an iridium complex, is presented.

Authors:
;  [1]
  1. Institute for Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 17, 1090 Vienna (Austria)
Publication Date:
OSTI Identifier:
22675961
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 2; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CALCULATION METHODS; COMPARATIVE EVALUATIONS; EXCITED STATES; IRIDIUM COMPLEXES; WAVE FUNCTIONS

Citation Formats

Plasser, Felix, E-mail: felix.plasser@univie.ac.at, and González, Leticia, E-mail: leticia.gonzalez@univie.ac.at. Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps. United States: N. p., 2016. Web. doi:10.1063/1.4958462.
Plasser, Felix, E-mail: felix.plasser@univie.ac.at, & González, Leticia, E-mail: leticia.gonzalez@univie.ac.at. Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps. United States. doi:10.1063/1.4958462.
Plasser, Felix, E-mail: felix.plasser@univie.ac.at, and González, Leticia, E-mail: leticia.gonzalez@univie.ac.at. Thu . "Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps". United States. doi:10.1063/1.4958462.
@article{osti_22675961,
title = {Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps},
author = {Plasser, Felix, E-mail: felix.plasser@univie.ac.at and González, Leticia, E-mail: leticia.gonzalez@univie.ac.at},
abstractNote = {A simple and powerful method for comparing many-electron wavefunctions constructed at different levels of theory is presented. By using wavefunction overlaps, it is possible to analyze the effects of varying wavefunction models, molecular orbitals, and one-electron basis sets. The computation of wavefunction overlaps eliminates the inherent ambiguity connected to more rudimentary wavefunction analysis protocols, such as visualization of orbitals or comparing selected physical observables. Instead, wavefunction overlaps allow processing the many-electron wavefunctions in their full inherent complexity. The presented method is particularly effective for excited state calculations as it allows for automatic monitoring of changes in the ordering of the excited states. A numerical demonstration based on multireference computations of two test systems, the selenoacrolein molecule and an iridium complex, is presented.},
doi = {10.1063/1.4958462},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 2,
volume = 145,
place = {United States},
year = {2016},
month = {7}
}