Ab Initio Investigation on the Second-Order Nonlinear Optical Responses in Keto-Enol Equilibria of Salicylideneanilines

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• 作者：Maxime Guillaume ; Benoî ; t Champagne ; Nadezhda Markova ; Venelin Enchev ; Fré ; dé ; ric Castet
• 刊名：Journal of Physical Chemistry A
• 出版年：2007
• 出版时间：October 4, 2007
• 年：2007
• 卷：111
• 期：39
• 页码：9914 - 9923
• 全文大小：200K
• 年卷期：v.111,no.39(October 4, 2007)
• ISSN：1520-5215

文摘

The keto-enol (K-E) tautomerization equilibrium, more precisely, the keto-amine/enol-imine equilibrium,has been investigated for a series of substituted salicylideneanilines in view of designing compounds with acontrast of second-order nonlinear optical properties. Substituting the salicylidene ring by an acceptor groupor the other ring by a donor prevents the K form from being stable, whereas in the other cases, the K formcan easily be converted to the E form due to the small activation barrier, figuring out in most cases that theK form is metastable. For a representative set of donor/acceptor substituents, the E and K forms present asufficiently large contrast of to allow its detection by using electric-field-induced second harmonic generationor hyper-Rayleigh scattering. The largest values are mainly associated with species bearing a donor in thepara position of the salicylidene ring and an acceptor on the other ring whereas the largest values aregenerally found for the E form.