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 trans VHF 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.
Original language | English |
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Pages (from-to) | 1349-1356 |
Number of pages | 8 |
Journal | New Journal of Chemistry |
Volume | 33 |
Issue number | 6 |
DOIs | |
Publication status | Published - 24 Jun 2009 |