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Title: A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

Abstract

A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg {sup 1}B{sub 1u} V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10{sup 9} parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the {sup 2}B{sub 3u} and {sup 2}B{sub 3} states were also determined. In addition, the heat of formation of twisted ethylene {sup 3}A{sub 1} was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.

Authors:
;  [1];  [2]
  1. Department of Chemistry, Washington State University, Pullman, Washington 99164-4630 (United States)
  2. Department of Chemistry, University of Washington, Seattle, Washington 98195-1700 (United States)
Publication Date:
OSTI Identifier:
22308365
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 10; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFIGURATION INTERACTION; ELECTRONS; ETHYLENE; EXCITED STATES; FORMATION HEAT; IONIZATION POTENTIAL; SENSITIVITY; TRIPLETS

Citation Formats

Feller, David, E-mail: dfeller@owt.com, Peterson, Kirk A., and Davidson, Ernest R. A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques. United States: N. p., 2014. Web. doi:10.1063/1.4894482.
Feller, David, E-mail: dfeller@owt.com, Peterson, Kirk A., & Davidson, Ernest R. A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques. United States. doi:10.1063/1.4894482.
Feller, David, E-mail: dfeller@owt.com, Peterson, Kirk A., and Davidson, Ernest R. Sun . "A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques". United States. doi:10.1063/1.4894482.
@article{osti_22308365,
title = {A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques},
author = {Feller, David, E-mail: dfeller@owt.com and Peterson, Kirk A. and Davidson, Ernest R.},
abstractNote = {A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg {sup 1}B{sub 1u} V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10{sup 9} parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the {sup 2}B{sub 3u} and {sup 2}B{sub 3} states were also determined. In addition, the heat of formation of twisted ethylene {sup 3}A{sub 1} was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.},
doi = {10.1063/1.4894482},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 10,
volume = 141,
place = {United States},
year = {2014},
month = {9}
}