Issue 6, 2009

Theoretical investigation of the dynamic first hyperpolarizability of DHA–VHF molecular switches

Abstract

The contrast of second-order nonlinear optical response in the dihydroazulene (DHA)-vinylheptafulvene (VHF) equilibrium has been investigated as a function of the nature of the substituent (R) on the phenyl ring by means of quantum chemistry calculations including electron correlation, frequency dispersion, and solvent effects. By considering the hyper-Rayleigh scattering (HRS) response, the contrast for R = H and R = CH3 between the DHA and VHF forms is larger than 5 while the contrast between the cis and transVHF forms is close to 1. Adding the NH2 donor group in para position of the phenyl leads to a substantial increase of the HRS first hyperpolarizability of the three forms, which is detrimental to the contrast. Then, in the case of the NO2 acceptor group, a contrast is recovered because the HRS first hyperpolarizability of the DHA form is about 2–3 times larger than for both VHF forms. These variations of first hyperpolarizability as a function of the substituents as well as the associated contrasts have been explained in terms of donor/acceptor strengths and geometrical parameters.

Graphical abstract: Theoretical investigation of the dynamic first hyperpolarizability of DHA–VHF molecular switches

Supplementary files

Article information

Article type
Paper
Submitted
08 Jan 2009
Accepted
19 Feb 2009
First published
31 Mar 2009

New J. Chem., 2009,33, 1349-1356

Theoretical investigation of the dynamic first hyperpolarizability of DHA–VHF molecular switches

A. Plaquet, B. Champagne, F. Castet, L. Ducasse, E. Bogdan, V. Rodriguez and J. Pozzo, New J. Chem., 2009, 33, 1349 DOI: 10.1039/B900432G

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