dc.contributor.author | Mavros, Michael G. | |
dc.contributor.author | Hait, Diptarka | |
dc.contributor.author | Van Voorhis, Troy | |
dc.contributor.author | Mavros, Michael George | |
dc.date.accessioned | 2018-04-30T18:09:08Z | |
dc.date.available | 2018-04-30T18:09:08Z | |
dc.date.issued | 2016-12 | |
dc.date.submitted | 2016-04 | |
dc.identifier.issn | 0021-9606 | |
dc.identifier.issn | 1089-7690 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/115106 | |
dc.description.abstract | Condensed phase electron transfer problems are often simplified by making the Condon approximation: the approximation that the coupling connecting two charge-transfer diabatic states is a constant. Unfortunately, the Condon approximation does not predict the existence of conical intersections, which are ubiquitous in both gas-phase and condensed-phase photochemical dynamics. In this paper, we develop a formalism to treat condensed-phase dynamics beyond the Condon approximation. We show that even for an extremely simple test system, hexaaquairon(ii)/hexaaquairon(iii) self-exchange in water, the electronic coupling is expected to fluctuate rapidly and non-Condon effects must be considered to obtain quantitatively accurate ultrafast nonequilibrium dynamics. As diabatic couplings are expected to fluctuate substantially in many condensed-phase electron transfer systems, non-Condon effects may be essential to quantitatively capture accurate short-time dynamics. | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) (Grant CHE-1464804) | en_US |
dc.language.iso | en_US | |
dc.publisher | American Chemical Society (ACS) | en_US |
dc.relation.isversionof | https://doi.org/10.1063/1.4971166 | 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 | Condensed phase electron transfer beyond the Condon approximation | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Mavros, Michael G. et al. “Condensed Phase Electron Transfer Beyond the Condon Approximation.” The Journal of Chemical Physics 145, 21 (December 2016): 214105 | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | |
dc.contributor.approver | Van Voorhis, Troy | en_US |
dc.contributor.mitauthor | Mavros, Michael George | |
dc.contributor.mitauthor | Hait, Diptarka | |
dc.contributor.mitauthor | Van Voorhis, Troy | |
dc.relation.journal | 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 | Mavros, Michael G.; Hait, Diptarka; Van Voorhis, Troy | en_US |
dspace.embargo.terms | N | en_US |
dc.identifier.orcid | https://orcid.org/0000-0002-7499-1017 | |
dc.identifier.orcid | https://orcid.org/0000-0001-7111-0176 | |