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Solvent Effects on Resonant First Hyperpolarizabilities and Raman and hyper-Raman Spectra of DANS and a Water-Soluble Analog

Solvent Effects on Resonant First Hyperpolarizabilities and Raman and hyper-Raman Spectra of DANS and a Water-Soluble Analog

Lian C T Shoute, Han Young Woo, Doojin Vak, Guillermo C Bazan, Anne Myers Kelley

J Chem Phys. 2006 Aug 7;125(5):054506.

PMID: 16942225

Abstract:

The two-photon-resonant first hyperpolarizabilities associated with hyper-Rayleigh and hyper-Raman scattering are reported for 4-dimethylamino-4-nitrostilbene in 1,4-dioxane, dichloromethane, acetonitrile, and methanol, and for an ionic analog, 4-N,N-bis(6-(N,N,N-trimethylammonium)-hexyl)amino-4-nitrostilbene dibromide in methanol and water. Resonance Raman and hyper-Raman excitation profiles are also measured and modeled. The resonance Raman and hyper-Raman spectra show very similar relative intensities which do not vary much as the excitation frequency is tuned across the lowest-energy strong linear absorption band, suggesting that a single resonant electronic state dominates the one- and two-photon absorptions in this region. The absorption, resonance Raman, and hyper-Raman profiles can be simulated reasonably well with a common set of parameters. The peak resonant (absolute value of beta)2, measured by hyper-Rayleigh scattering, varies by about 50% over the range of solvents examined and shows a weak correlation with the linear absorption maximum, with the redder-absorbing systems exhibiting larger peak hyperpolarizabilities. The experimental hyper-Rayleigh intensities are higher than those calculated, possibly reflecting contributions from nonresonant electronic states.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP2844157	4-Dimethylamino-4′-nitrostilbene		2844-15-7	Price

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