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Title: Driven similarity renormalization group for excited states: A state-averaged perturbation theory

Abstract

The multireference driven similarity renormalization group (MRDSRG) approach [C. Li and F. A. Evangelista, J. Chem. Theory Comput. 11, 2097 (2015)] is generalized to treat quasi-degenerate electronic excited states. The new scheme, termed state-averaged (SA) MRDSRG, is a state-universal approach that considers an ensemble of quasi-degenerate states on an equal footing. Using the SA-MRDSRG framework, we implement second- (SA-DSRG-PT2) and third-order (SA-DSRG-PT3) perturbation theories. These perturbation theories can treat a manifold of near-degenerate states at the cost of a single state-specific computation. At the same time, they have several desirable properties: (1) they are intruder-free and size-extensive, (2) their energy expressions can be evaluated non-iteratively and require at most the three-body density cumulant of the reference states, and (3) the reference states are allowed to relax in the presence of dynamical correlation effects. Numerical benchmarks on the potential energy surfaces of lithium fluoride, ammonia, and the penta-2,4-dieniminium cation reveal that the SA-DSRG-PT2 method yields results with accuracy similar to that of other second-order quasi-degenerate perturbation theories. The SA-DSRG-PT3 results are instead consistent with those from multireference configuration interaction with singles and doubles (MRCISD). Finally, we compute the vertical excitation energies of (E,E)-1,3,5,7-octatetraene. As a result, the ordering of the lowestmore » three states is predicted to be 21A g <1 1B +u <1 1B u by both SA-DSRG-PT2 and SA-DSRG-PT3, in accordance with MRCISD plus Davidson correction.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1511175
Alternate Identifier(s):
OSTI ID: 1429144
Grant/Contract Number:  
SC0016004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 12; 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

Citation Formats

Li, Chenyang, and Evangelista, Francesco A. Driven similarity renormalization group for excited states: A state-averaged perturbation theory. United States: N. p., 2018. Web. doi:10.1063/1.5019793.
Li, Chenyang, & Evangelista, Francesco A. Driven similarity renormalization group for excited states: A state-averaged perturbation theory. United States. https://doi.org/10.1063/1.5019793
Li, Chenyang, and Evangelista, Francesco A. 2018. "Driven similarity renormalization group for excited states: A state-averaged perturbation theory". United States. https://doi.org/10.1063/1.5019793. https://www.osti.gov/servlets/purl/1511175.
@article{osti_1511175,
title = {Driven similarity renormalization group for excited states: A state-averaged perturbation theory},
author = {Li, Chenyang and Evangelista, Francesco A.},
abstractNote = {The multireference driven similarity renormalization group (MRDSRG) approach [C. Li and F. A. Evangelista, J. Chem. Theory Comput. 11, 2097 (2015)] is generalized to treat quasi-degenerate electronic excited states. The new scheme, termed state-averaged (SA) MRDSRG, is a state-universal approach that considers an ensemble of quasi-degenerate states on an equal footing. Using the SA-MRDSRG framework, we implement second- (SA-DSRG-PT2) and third-order (SA-DSRG-PT3) perturbation theories. These perturbation theories can treat a manifold of near-degenerate states at the cost of a single state-specific computation. At the same time, they have several desirable properties: (1) they are intruder-free and size-extensive, (2) their energy expressions can be evaluated non-iteratively and require at most the three-body density cumulant of the reference states, and (3) the reference states are allowed to relax in the presence of dynamical correlation effects. Numerical benchmarks on the potential energy surfaces of lithium fluoride, ammonia, and the penta-2,4-dieniminium cation reveal that the SA-DSRG-PT2 method yields results with accuracy similar to that of other second-order quasi-degenerate perturbation theories. The SA-DSRG-PT3 results are instead consistent with those from multireference configuration interaction with singles and doubles (MRCISD). Finally, we compute the vertical excitation energies of (E,E)-1,3,5,7-octatetraene. As a result, the ordering of the lowest three states is predicted to be 21A –g <1 1B +u <1 1B –u by both SA-DSRG-PT2 and SA-DSRG-PT3, in accordance with MRCISD plus Davidson correction.},
doi = {10.1063/1.5019793},
url = {https://www.osti.gov/biblio/1511175}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 12,
volume = 148,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 6 works
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Figures / Tables:

FIG. 1 FIG. 1: Potential energy curves for the lowest two 1$$Σ$$+ states of lithium fluoride computed using various methods and the aug(F)-cc-pVTZ basis set. For each method, a circle marks the average energy of the two states at the bond length with the smallest energy gap.

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Works referencing / citing this record:

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.