Solvent intermolecular polarizability response in solvation
Polarizability response spectroscopy, a two-color optical Kerr effect method, has been developed and employed to study solvent intermolecular polarizability responses to photoexcited solutes. Here, we report solvent intermolecular polarizability responses in (dipolar) solvation. The time-resolved no...
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Veröffentlicht in: | The Journal of chemical physics 2003-03, Vol.118 (9), p.3917-3920 |
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Hauptverfasser: | , , , , , |
Format: | Artikel |
Sprache: | eng |
Online-Zugang: | Volltext |
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Zusammenfassung: | Polarizability response spectroscopy, a two-color optical Kerr effect method, has been developed and employed to study solvent intermolecular polarizability responses to photoexcited solutes. Here, we report solvent intermolecular polarizability responses in (dipolar) solvation. The time-resolved nonresonant polarizability signals are analyzed in the frequency domain where they are fit to a functional form representing diffusive reorientational, interaction-induced, and librational motions. Diffusive reorientational motion of CHCl3 was preferentially driven following photoexcitation of Coumarin 153 while interaction-induced motion was mainly driven in CH3CN solutions. The mechanism for selective solvent responses involves the relative orientation of the solvent dipole and most polarizable molecular axes and their interaction strength to the solute dipole. |
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ISSN: | 0021-9606 1089-7690 |
DOI: | 10.1063/1.1555804 |