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Title: Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data

Abstract

Singlet–triplet gaps in diradical organic π-systems are of interest in many applications. In this work, we calculate them in a series of molecules, including cyclobutadiene and its derivatives and cyclopentadienyl cation, by using correlated participating orbitals within the complete active space (CAS) and restricted active space (RAS) self-consistent field frameworks, followed by second-order perturbation theory (CASPT2 and RASPT2). These calculations are evaluated by comparison with the results of doubly electron-attached (DEA) equation-of-motion (EOM) coupled-cluster (CC) calculations with up to 4-particle–2-hole (4p-2h) excitations. Finally, we find active spaces that can accurately reproduce the DEA-EOMCC(4p-2h) data while being small enough to be applicable to larger organic diradicals.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
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  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Michigan State Univ., East Lansing, MI (United States)
Publication Date:
Research Org.:
Michigan State Univ., East Lansing, MI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1512954
Grant/Contract Number:  
FG02-01ER15228
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 16; 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

Stoneburner, Samuel J., Shen, Jun, Ajala, Adeayo O., Piecuch, Piotr, Truhlar, Donald G., and Gagliardi, Laura. Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data. United States: N. p., 2017. Web. doi:10.1063/1.4998256.
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Stoneburner, Samuel J., Shen, Jun, Ajala, Adeayo O., Piecuch, Piotr, Truhlar, Donald G., & Gagliardi, Laura. Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data. United States. doi:10.1063/1.4998256.
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Stoneburner, Samuel J., Shen, Jun, Ajala, Adeayo O., Piecuch, Piotr, Truhlar, Donald G., and Gagliardi, Laura. Tue . "Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data". United States. doi:10.1063/1.4998256. https://www.osti.gov/servlets/purl/1512954.
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@article{osti_1512954,
title = {Systematic design of active spaces for multi-reference calculations of singlet–triplet gaps of organic diradicals, with benchmarks against doubly electron-attached coupled-cluster data},
author = {Stoneburner, Samuel J. and Shen, Jun and Ajala, Adeayo O. and Piecuch, Piotr and Truhlar, Donald G. and Gagliardi, Laura},
abstractNote = {Singlet–triplet gaps in diradical organic π-systems are of interest in many applications. In this work, we calculate them in a series of molecules, including cyclobutadiene and its derivatives and cyclopentadienyl cation, by using correlated participating orbitals within the complete active space (CAS) and restricted active space (RAS) self-consistent field frameworks, followed by second-order perturbation theory (CASPT2 and RASPT2). These calculations are evaluated by comparison with the results of doubly electron-attached (DEA) equation-of-motion (EOM) coupled-cluster (CC) calculations with up to 4-particle–2-hole (4p-2h) excitations. Finally, we find active spaces that can accurately reproduce the DEA-EOMCC(4p-2h) data while being small enough to be applicable to larger organic diradicals.},
doi = {10.1063/1.4998256},
journal = {Journal of Chemical Physics},
number = 16,
volume = 147,
place = {United States},
year = {2017},
month = {10}
}
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DOI:  10.1063/1.4998256
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Cited by: 9 works
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Figures / Tables:

FIG. 1 FIG. 1: Diradical systems under investigation. 1: C4H4, 2: C5H5+, 3: C4H3NH2, 4: C4H3CHO, 5: C4H2NH2CHO, 6: C4H2-1,2-(CH2)2, 7: C4H21,3-(CH2)2.
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      TABLE I (p. 7)table
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      TABLE IV (p. 10)table
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