A new approach to approximate equation-of-motion coupled cluster with triple excitations
Abstract
Accurate methods for excited, ionized, and electron-attached states are critical to the study of many chemical species such as reactive intermediates, radicals, and ionized systems. The equation-of-motion coupled cluster singles, doubles, and triples (EOM-CCSDT) family of methods is very accurate (roughly similar in accuracy as for CCSDT calculations of the ground state), but the computational cost scales iteratively as the eighth power of the system size. Many approximations already exist, although most either correct only the excited state or require an iterative $$\mathscr{O}$$(n7) procedure which can also be prohibitively expensive. In this paper, new methods, termed EOM-CCSD(T)(a) and EOM-CCSD(T)(a)*, are proposed which correct both the ground and excited states based on a shared effective Hamiltonian, and the latter of which includes only non-iterative corrections to both the CCSD and EOM-CCSD energies. These methods are found to significantly improve the description of excited and ionized potential energy surfaces, equilibrium geometries, and harmonic frequencies; the accuracy is very close to that of full EOM-CCSDT.
- Authors:
-
- Univ. of Texas, Austin, TX (United States). Inst. for Computational Engineering and Sciences
- Univ. of Texas, Austin, TX (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States). Inst. for Computational Engineering and Sciences
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1468931
- Alternate Identifier(s):
- OSTI ID: 1326117
- Grant/Contract Number:
- FG02-07ER15884
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 145; 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
Matthews, Devin A., and Stanton, John F. A new approach to approximate equation-of-motion coupled cluster with triple excitations. United States: N. p., 2016.
Web. doi:10.1063/1.4962910.
Matthews, Devin A., & Stanton, John F. A new approach to approximate equation-of-motion coupled cluster with triple excitations. United States. https://doi.org/10.1063/1.4962910
Matthews, Devin A., and Stanton, John F. Wed .
"A new approach to approximate equation-of-motion coupled cluster with triple excitations". United States. https://doi.org/10.1063/1.4962910. https://www.osti.gov/servlets/purl/1468931.
@article{osti_1468931,
title = {A new approach to approximate equation-of-motion coupled cluster with triple excitations},
author = {Matthews, Devin A. and Stanton, John F.},
abstractNote = {Accurate methods for excited, ionized, and electron-attached states are critical to the study of many chemical species such as reactive intermediates, radicals, and ionized systems. The equation-of-motion coupled cluster singles, doubles, and triples (EOM-CCSDT) family of methods is very accurate (roughly similar in accuracy as for CCSDT calculations of the ground state), but the computational cost scales iteratively as the eighth power of the system size. Many approximations already exist, although most either correct only the excited state or require an iterative $\mathscr{O}$(n7) procedure which can also be prohibitively expensive. In this paper, new methods, termed EOM-CCSD(T)(a) and EOM-CCSD(T)(a)*, are proposed which correct both the ground and excited states based on a shared effective Hamiltonian, and the latter of which includes only non-iterative corrections to both the CCSD and EOM-CCSD energies. These methods are found to significantly improve the description of excited and ionized potential energy surfaces, equilibrium geometries, and harmonic frequencies; the accuracy is very close to that of full EOM-CCSDT.},
doi = {10.1063/1.4962910},
journal = {Journal of Chemical Physics},
number = 12,
volume = 145,
place = {United States},
year = {Wed Sep 28 00:00:00 EDT 2016},
month = {Wed Sep 28 00:00:00 EDT 2016}
}
Web of Science
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