Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST )
Abstract
CASSCF and CASPT2 calculations have been performed on the triplet and two lowest-lying singlet states of the 2,7-naphthoquinodimethane (NQDM) and 2,7-naphthoquinone (NQ) diradicals. Both diradicals are predicted to have triplet ground states but to differ in the ordering of the two lowest singlet states, with E(1A1) < E(1B2) in NQDM, but E(1A1) > E(1B2) in NQ. The reason for the difference in ordering of the singlet states in these two diradicals is discussed. The state reordering is shown to be responsible for the prediction that the substitution of the oxygens in NQ for the CH2 groups in NQDM increases, rather than decreases, the singlet-triplet energy separation (EST).
- Authors:
-
- Department of Chemistry and the Center for Advanced, Scientific Computing and Modeling, University of North Texas, Denton TX USA
- Physical Sciences Division, Pacific Northwest National Laboratory, Richland WA USA
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1508275
- Report Number(s):
- PNNL-SA-131464
Journal ID: ISSN 0894-3230
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Physical Organic Chemistry
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 8; Journal ID: ISSN 0894-3230
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Hrovat, David A., Wang, Xue-Bin, and Borden, Weston Thatcher. Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST ). United States: N. p., 2018.
Web. doi:10.1002/poc.3824.
Hrovat, David A., Wang, Xue-Bin, & Borden, Weston Thatcher. Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST ). United States. https://doi.org/10.1002/poc.3824
Hrovat, David A., Wang, Xue-Bin, and Borden, Weston Thatcher. 2018.
"Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST )". United States. https://doi.org/10.1002/poc.3824.
@article{osti_1508275,
title = {Calculations of the relative energies of the low-lying electronic states of 2,7-naphthoquinodimethane and 2,7-naphthoquinone. Substitution of oxygen for CH 2 is predicted to increase the singlet-triplet energy difference ( ΔE ST )},
author = {Hrovat, David A. and Wang, Xue-Bin and Borden, Weston Thatcher},
abstractNote = {CASSCF and CASPT2 calculations have been performed on the triplet and two lowest-lying singlet states of the 2,7-naphthoquinodimethane (NQDM) and 2,7-naphthoquinone (NQ) diradicals. Both diradicals are predicted to have triplet ground states but to differ in the ordering of the two lowest singlet states, with E(1A1) < E(1B2) in NQDM, but E(1A1) > E(1B2) in NQ. The reason for the difference in ordering of the singlet states in these two diradicals is discussed. The state reordering is shown to be responsible for the prediction that the substitution of the oxygens in NQ for the CH2 groups in NQDM increases, rather than decreases, the singlet-triplet energy separation (EST).},
doi = {10.1002/poc.3824},
url = {https://www.osti.gov/biblio/1508275},
journal = {Journal of Physical Organic Chemistry},
issn = {0894-3230},
number = 8,
volume = 31,
place = {United States},
year = {Tue Feb 20 00:00:00 EST 2018},
month = {Tue Feb 20 00:00:00 EST 2018}
}
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