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Importance of a low-lying nπ*-state in the photo-isomerisation reaction of Z-methylfurylfulgide

Paper ID Volume ID Publish Year Pages File Format Full-Text
27026 43995 2013 7 PDF Available
Title
Importance of a low-lying nπ*-state in the photo-isomerisation reaction of Z-methylfurylfulgide
Abstract

•nπ*-Character is present in S1 and S2 at the Z-Franck–Condon point.•Excited state character quickly changes on the path Z→E.•There is no nπ*-character in S1 close to the conical intersection.•These findings significantly differ from older findings for E→Z and E↔C.

Knowledge about the character of electronic states involved in ultrafast photoreactions is essential for understanding the dynamics leading to static and transient experimental spectra. Here we present a detailed study of the three lowest-energy electronic states of the photochromic switch methylfurylfulgide in its Z-form and of their changes as they approach the S1S0-conical intersection that facilitates the formation of E-methylfurylfulgide. We studied the molecular energy landscape by identifying important points along the reaction coordinate (Franck–Condon point, S1-energy minimum and S1S0-conical intersection) by state-averaged CASSCF(10,9)/6-31g(d,p) calculations, assigned the character of the three lowest electronic states at these points and verified our classifications by CASPT2(18,13) calculations in a basis of polarised triple-zeta quality for the atoms relevant to the reaction and polarised double-zeta for the others. In contrast to the E→Z interconversion, it turns out that a proper active space for the Z→E interconversion should consist not only of π orbitals but should contain also orbitals of n character. We expect this to experimentally manifest itself in visible differences between Z→E and E→Z behaviour.

Keywords
CASSCF; CASPT2; Multi-reference; Excited states; Photoswitches
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Importance of a low-lying nπ*-state in the photo-isomerisation reaction of Z-methylfurylfulgide
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Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 263, 1 July 2013, Pages 34–40
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us