dc.contributor.author | Kaduk, Benjamin James | |
dc.contributor.author | Tsuchimochi, Takashi | |
dc.contributor.author | Van Voorhis, Troy | |
dc.date.accessioned | 2015-03-30T17:53:18Z | |
dc.date.available | 2015-03-30T17:53:18Z | |
dc.date.issued | 2014-01 | |
dc.date.submitted | 2013-10 | |
dc.identifier.issn | 0021-9606 | |
dc.identifier.issn | 1089-7690 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/96256 | |
dc.description.abstract | 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. | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) (CAREER Award CHE-0547877) | en_US |
dc.description.sponsorship | David & Lucile Packard Foundation (Fellowship) | en_US |
dc.language.iso | en_US | |
dc.publisher | American Institute of Physics (AIP) | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1063/1.4862497 | en_US |
dc.rights | Creative Commons Attribution-Noncommercial-Share Alike | en_US |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-sa/4.0/ | en_US |
dc.source | Prof. Van Voorhis via Erja Kajosalo | en_US |
dc.title | Analytic energy gradients for constrained DFT-configuration interaction | en_US |
dc.type | Article | en_US |
dc.identifier.citation | 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. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.mitauthor | Kaduk, Benjamin James | en_US |
dc.contributor.mitauthor | Tsuchimochi, Takashi | en_US |
dc.contributor.mitauthor | Van Voorhis, Troy | en_US |
dc.relation.journal | The Journal of Chemical Physics | en_US |
dc.eprint.version | Author's final manuscript | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Kaduk, Benjamin; Tsuchimochi, Takashi; Van Voorhis, Troy | en_US |
dc.identifier.orcid | https://orcid.org/0000-0001-7111-0176 | |
mit.license | OPEN_ACCESS_POLICY | en_US |
mit.metadata.status | Complete | |