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Title: Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods

Abstract

In this paper, we introduce two new approaches to compute near-degenerate electronic states based on the driven similarity renormalization group (DSRG) framework. The first approach is a unitary multi-state formalism based on the DSRG (MS-DSRG), whereby an effective Hamiltonian is built from a set of state-specific solutions. The second approach employs a dynamic weighting parameter to smoothly interpolate between the multi-state and the state-averaged DSRG schemes. The resulting dynamically weighted DSRG (DW-DSRG) theory incorporates the most desirable features of both multi-state approaches (ability to accurately treat many states) and state-averaged methods (correct description of avoided crossings and conical intersections). We formulate second-order perturbation theories (PT2) based on the MS- and DW-DSRG and study the potential energy curves of LiF, the conical intersection of the two lowest singlet states of NH 3, and several low-lying excited states of benzene, naphthalene, and anthracene. The DW-DSRG-PT2 predicts the correct avoided crossing of LiF and avoids artifacts produced by the corresponding state-specific and multi-state theories. Excitation energies of the acenes computed with the DW-DSRG-PT2 are found to be more accurate than the corresponding state-averaged values, showing a small dependence on the number of states computed.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Emory Univ., Atlanta, GA (United States)
  2. Uppsala Univ. (Sweden)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Alfred P. Sloan Foundation; Swedish Research Council (VR); National Science Foundation (NSF); Wenner-Gren Foundation
OSTI Identifier:
1612369
Alternate Identifier(s):
OSTI ID: 1505880
Grant/Contract Number:  
SC0016004; 2016-03398; CHE-1464862
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics; Potential energy surfaces; Excitation energies; Renormalization and regularization; Density-matrix; Degenerate energy levels; Perturbation theory

Citation Formats

Li, Chenyang, Lindh, Roland, and Evangelista, Francesco A. Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods. United States: N. p., 2019. Web. doi:10.1063/1.5088120.
Li, Chenyang, Lindh, Roland, & Evangelista, Francesco A. Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods. United States. doi:10.1063/1.5088120.
Li, Chenyang, Lindh, Roland, and Evangelista, Francesco A. Tue . "Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods". United States. doi:10.1063/1.5088120. https://www.osti.gov/servlets/purl/1612369.
@article{osti_1612369,
title = {Dynamically weighted multireference perturbation theory: Combining the advantages of multi-state and state-averaged methods},
author = {Li, Chenyang and Lindh, Roland and Evangelista, Francesco A.},
abstractNote = {In this paper, we introduce two new approaches to compute near-degenerate electronic states based on the driven similarity renormalization group (DSRG) framework. The first approach is a unitary multi-state formalism based on the DSRG (MS-DSRG), whereby an effective Hamiltonian is built from a set of state-specific solutions. The second approach employs a dynamic weighting parameter to smoothly interpolate between the multi-state and the state-averaged DSRG schemes. The resulting dynamically weighted DSRG (DW-DSRG) theory incorporates the most desirable features of both multi-state approaches (ability to accurately treat many states) and state-averaged methods (correct description of avoided crossings and conical intersections). We formulate second-order perturbation theories (PT2) based on the MS- and DW-DSRG and study the potential energy curves of LiF, the conical intersection of the two lowest singlet states of NH3, and several low-lying excited states of benzene, naphthalene, and anthracene. The DW-DSRG-PT2 predicts the correct avoided crossing of LiF and avoids artifacts produced by the corresponding state-specific and multi-state theories. Excitation energies of the acenes computed with the DW-DSRG-PT2 are found to be more accurate than the corresponding state-averaged values, showing a small dependence on the number of states computed.},
doi = {10.1063/1.5088120},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 14,
volume = 150,
place = {United States},
year = {2019},
month = {4}
}

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