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:
-
[1];
[2];
[1];
[1]
- Univ. of Minnesota, Minneapolis, MN (United States)
- 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.
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.
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.
@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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