uu.seUppsala University Publications
Change search
ReferencesLink to record
Permanent link

Direct link
Dynamic Electron Correlation Effects on the Ground State Potential Energy Surface of a Retinal Chromophore Model
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-7567-8295
Show others and affiliations
2012 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 8, no 11, 4069-4080 p.Article in journal (Refereed) Published
Abstract [en]

The ground state potential energy surface of the retinal chromophore of visual pigments (e.g., bovine rhodopsin) features a low-lying conical intersection surrounded by regions with variable charge-transfer and diradical electronic structures. This implies that dynamic electron correlation may have a large effect on the shape of the force fields driving its reactivity. To investigate this effect, we focus on mapping the potential energy for three paths located along the ground state CASSCF potential energy surface of the penta-2,4-dieniminium cation taken as a minimal model of the retinal chromophore. The first path spans the bond length alternation coordinate and intercepts a conical intersection point. The other two are minimum energy paths along two distinct but kinetically competitive thermal isomerization coordinates. We show that the effect of introducing the missing dynamic electron correlation variationally (with MRCISD) and perturbatively (with the CASPT2, NEVPT2, and XMCQDPT2 methods) leads, invariably, to a stabilization of the regions with charge transfer character and to a significant reshaping of the reference CASSCF potential energy surface and suggesting a change in the dominating isomerization mechanism. The possible impact of such a correction on the photoisomerization of the retinal chromophore is discussed.

Place, publisher, year, edition, pages
2012. Vol. 8, no 11, 4069-4080 p.
National Category
Theoretical Chemistry
URN: urn:nbn:se:uu:diva-181529DOI: 10.1021/ct3003139ISI: 000311191900010OAI: oai:DiVA.org:uu-181529DiVA: diva2:556533
Available from: 2012-09-25 Created: 2012-09-25 Last updated: 2015-01-08Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full texthttp://pubs.acs.org/doi/abs/10.1021/ct3003139

Search in DiVA

By author/editor
Lindh, Roland
By organisation
Theoretical Chemistry
In the same journal
Journal of Chemical Theory and Computation
Theoretical Chemistry

Search outside of DiVA

GoogleGoogle Scholar
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

Altmetric score

Total: 459 hits
ReferencesLink to record
Permanent link

Direct link