| dc.contributor |
Massachusetts Institute of Technology. Department of Chemistry |
|
| dc.contributor |
Kaduk, Benjamin James |
|
| dc.contributor |
Tsuchimochi, Takashi |
|
| dc.contributor |
Van Voorhis, Troy |
|
| dc.creator |
Kaduk, Benjamin James |
|
| dc.creator |
Tsuchimochi, Takashi |
|
| dc.creator |
Van Voorhis, Troy |
|
| dc.date |
2015-03-30T17:53:18Z |
|
| dc.date |
2015-03-30T17:53:18Z |
|
| dc.date |
2014-01 |
|
| dc.date |
2013-10 |
|
| dc.date.accessioned |
2023-03-01T18:07:46Z |
|
| dc.date.available |
2023-03-01T18:07:46Z |
|
| dc.identifier |
0021-9606 |
|
| dc.identifier |
1089-7690 |
|
| dc.identifier |
http://hdl.handle.net/1721.1/96256 |
|
| dc.identifier |
Kaduk, Benjamin, Takashi Tsuchimochi, and Troy Van Voorhis. “Analytic Energy Gradients for Constrained DFT-Configuration Interaction.” The Journal of Chemical Physics 140, no. 18 (May 14, 2014): 18A503. |
|
| dc.identifier |
https://orcid.org/0000-0001-7111-0176 |
|
| dc.identifier.uri |
http://localhost:8080/xmlui/handle/CUHPOERS/278858 |
|
| dc.description |
The constrained density functional theory-configuration interaction (CDFT-CI) method has previously been used to calculate ground-state energies and barrier heights, and to describe electronic excited states, in particular conical intersections. However, the method has been limited to evaluating the electronic energy at just a single nuclear configuration, with the gradient of the energy being available only via finite difference. In this paper, we present analytic gradients of the CDFT-CI energy with respect to nuclear coordinates, which gives the potential for accurate geometry optimization and molecular dynamics on both the ground and excited electronic states, a realm which is currently quite challenging for electronic structure theory. We report the performance of CDFT-CI geometry optimization for representative reaction transition states as well as molecules in an excited state. The overall accuracy of CDFT-CI for computing barrier heights is essentially unchanged whether the energies are evaluated at geometries obtained from quadratic configuration-interaction singles and doubles (QCISD) or CDFT-CI, indicating that CDFT-CI produces very good reaction transition states. These results open up tantalizing possibilities for future work on excited states. |
|
| dc.description |
National Science Foundation (U.S.) (CAREER Award CHE-0547877) |
|
| dc.description |
David & Lucile Packard Foundation (Fellowship) |
|
| dc.format |
application/pdf |
|
| dc.language |
en_US |
|
| dc.publisher |
American Institute of Physics (AIP) |
|
| dc.relation |
http://dx.doi.org/10.1063/1.4862497 |
|
| dc.relation |
The Journal of Chemical Physics |
|
| dc.rights |
Creative Commons Attribution-Noncommercial-Share Alike |
|
| dc.rights |
http://creativecommons.org/licenses/by-nc-sa/4.0/ |
|
| dc.source |
Prof. Van Voorhis via Erja Kajosalo |
|
| dc.title |
Analytic energy gradients for constrained DFT-configuration interaction |
|
| dc.type |
Article |
|
| dc.type |
http://purl.org/eprint/type/JournalArticle |
|