skip to main content

DOE PAGESDOE PAGES

Title: A time-dependent formulation of multi-reference perturbation theory

Here, we discuss the time-dependent formulation of perturbation theory in the context of the interacting zeroth-order Hamiltonians that appear in multi-reference situations. As an example, we present a time-dependent formulation and implementation of second-order n-electron valence perturbation theory. The resulting time-dependent n-electron valence second-order perturbation theory (t-NEVPT2) method yields the fully uncontracted n-electron valence perturbation wavefunction and energy, but has a lower computational scaling than the usual contracted variants, and also avoids the construction of high-order density matrices and the diagonalization of metrics.We present results of t-NEVPT2 for the water, nitrogen, carbon, and chromium molecules and outline directions for the future.
Authors:
 [1] ;  [1]
  1. Princeton Univ., Princeton, NJ (United States)
Publication Date:
Grant/Contract Number:
SC0008624; SC0010530
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Princeton Univ., NJ (United States)
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1469673
Alternate Identifier(s):
OSTI ID: 1237776

Sokolov, Alexander Yu., and Chan, Garnet Kin-Lic. A time-dependent formulation of multi-reference perturbation theory. United States: N. p., Web. doi:10.1063/1.4941606.
Sokolov, Alexander Yu., & Chan, Garnet Kin-Lic. A time-dependent formulation of multi-reference perturbation theory. United States. doi:10.1063/1.4941606.
Sokolov, Alexander Yu., and Chan, Garnet Kin-Lic. 2016. "A time-dependent formulation of multi-reference perturbation theory". United States. doi:10.1063/1.4941606. https://www.osti.gov/servlets/purl/1469673.
@article{osti_1469673,
title = {A time-dependent formulation of multi-reference perturbation theory},
author = {Sokolov, Alexander Yu. and Chan, Garnet Kin-Lic},
abstractNote = {Here, we discuss the time-dependent formulation of perturbation theory in the context of the interacting zeroth-order Hamiltonians that appear in multi-reference situations. As an example, we present a time-dependent formulation and implementation of second-order n-electron valence perturbation theory. The resulting time-dependent n-electron valence second-order perturbation theory (t-NEVPT2) method yields the fully uncontracted n-electron valence perturbation wavefunction and energy, but has a lower computational scaling than the usual contracted variants, and also avoids the construction of high-order density matrices and the diagonalization of metrics.We present results of t-NEVPT2 for the water, nitrogen, carbon, and chromium molecules and outline directions for the future.},
doi = {10.1063/1.4941606},
journal = {Journal of Chemical Physics},
number = 6,
volume = 144,
place = {United States},
year = {2016},
month = {2}
}