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• W2036622690 abstract "The solvation dynamics following photoexcitation of chlorine dioxide (OClO) in different solvents are investigated by classical molecular dynamics. Following previous work on the aqueous response to OClO photoexcitation [J. Chem. Phys. 118, 4563 (2003)], the present study considers the response of chloroform and cyclohexane; these three liquids present unique solvent environments that differ significantly in both polarity and structure. The study is designed to ascertain the origin of the solvent-invariant homogeneous linewidth associated with OClO photoexcitation and to confirm, at the molecular level, whether the relaxation dynamics are similar across dissimilar solvents due to chance or a common relaxation origin. The results obtained here are used to predict the time scale of solvent-induced optical dephasing, and excellent agreement with experiment is observed for all solvents. Analysis demonstrates that the solvation dynamics of OClO are dominated by short-ranged mechanical solute–solvent interactions regardless of the identity and electrostatic properties of the solvent. Low-frequency translational motions dominate the coupling spectrum, and virtually no contribution to energy gap relaxation is achieved through intramolecular solvent motions. The invariant homogeneous linewidth is attributed to the similarity in the primary response of all solvents to OClO photoexcitation." @default.
• W2036622690 created "2016-06-24" @default.
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• W2036622690 date "2003-10-17" @default.
• W2036622690 modified "2023-10-14" @default.
• W2036622690 title "Molecular dynamics study of the weakly solvent dependent relaxation dynamics following chlorine dioxide photoexcitation" @default.
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• W2036622690 doi "https://doi.org/10.1063/1.1614203" @default.
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