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Title: Using reduced density matrix techniques to capture static and dynamic correlation in the energy landscape for the decomposition of the CH 2 CH 2 ONO radical and support a non-IRC pathway

Abstract

The unexpected abundance of HNO in the photodecomposition of the radical 2-nitrosooxy ethyl (CH2CH2ONO) is investigated through calculations of the potential energy surface by the anti-Hermitian contracted Schrödinger equation (ACSE) method, which directly generates the 2-electron reduced density matrix. The ACSE, which is able to balance single-reference (dynamic) and multi-reference (static) correlation effects, reveals some subtle correlation effects along the intrinsic reaction coordinate (IRC) en route to NO + oxirane, an IRC which offers a potential bifurcation to the HNO + vinoxy product channel. These effects were not fully captured by either single-reference techniques, such as coupled cluster, or multi-reference techniques, such as second-order multi-reference perturbation theory. These correlation effects reveal small to moderate energy changes in key transition states, which have implications for the reaction mechanism as related to the production of HNO.

Authors:
ORCiD logo [1];  [1];  [1];  [1]
  1. The James Franck Institute and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1540177
Alternate Identifier(s):
OSTI ID: 1459692
Grant/Contract Number:  
FG02-92ER14305
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Physics

Citation Formats

Smart, Scott E., Scrape, Preston G., Butler, Laurie J., and Mazziotti, David A. Using reduced density matrix techniques to capture static and dynamic correlation in the energy landscape for the decomposition of the CH 2 CH 2 ONO radical and support a non-IRC pathway. United States: N. p., 2018. Web. doi:10.1063/1.5024512.
Smart, Scott E., Scrape, Preston G., Butler, Laurie J., & Mazziotti, David A. Using reduced density matrix techniques to capture static and dynamic correlation in the energy landscape for the decomposition of the CH 2 CH 2 ONO radical and support a non-IRC pathway. United States. doi:10.1063/1.5024512.
Smart, Scott E., Scrape, Preston G., Butler, Laurie J., and Mazziotti, David A. Sat . "Using reduced density matrix techniques to capture static and dynamic correlation in the energy landscape for the decomposition of the CH 2 CH 2 ONO radical and support a non-IRC pathway". United States. doi:10.1063/1.5024512. https://www.osti.gov/servlets/purl/1540177.
@article{osti_1540177,
title = {Using reduced density matrix techniques to capture static and dynamic correlation in the energy landscape for the decomposition of the CH 2 CH 2 ONO radical and support a non-IRC pathway},
author = {Smart, Scott E. and Scrape, Preston G. and Butler, Laurie J. and Mazziotti, David A.},
abstractNote = {The unexpected abundance of HNO in the photodecomposition of the radical 2-nitrosooxy ethyl (CH2CH2ONO) is investigated through calculations of the potential energy surface by the anti-Hermitian contracted Schrödinger equation (ACSE) method, which directly generates the 2-electron reduced density matrix. The ACSE, which is able to balance single-reference (dynamic) and multi-reference (static) correlation effects, reveals some subtle correlation effects along the intrinsic reaction coordinate (IRC) en route to NO + oxirane, an IRC which offers a potential bifurcation to the HNO + vinoxy product channel. These effects were not fully captured by either single-reference techniques, such as coupled cluster, or multi-reference techniques, such as second-order multi-reference perturbation theory. These correlation effects reveal small to moderate energy changes in key transition states, which have implications for the reaction mechanism as related to the production of HNO.},
doi = {10.1063/1.5024512},
journal = {Journal of Chemical Physics},
number = 2,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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Works referenced in this record:

Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972

  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
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