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dc.contributor.authorTrimithioti, Marilenaen
dc.contributor.authorAkimov, A. V.en
dc.contributor.authorPrezhdo, O. V.en
dc.contributor.authorHayes, Sophia C.en
dc.creatorTrimithioti, Marilenaen
dc.creatorAkimov, A. V.en
dc.creatorPrezhdo, O. V.en
dc.creatorHayes, Sophia C.en
dc.description.abstractA detailed analysis of the resonance Raman depolarization ratio dispersion curve for the N-O symmetric stretch of nitryl chloride in methanol at excitation wavelengths spanning the D absorption band is presented. The depolarization ratios are modeled using the time-dependent formalism for Raman scattering with contributions from two excited states (21A1 and 3 1B1), which are taken as linearly dissociative along the Cl-N coordinate. The analysis focuses on the interplay between different types of broadening revealing the importance of inhomogenous broadening in determining the relative contributions of the two electronic transitions. We find that the transition dipole moment (M) for 21A1 is greater than for 31B1, in agreement with gas phase calculations in the literature A. Lesar, M. Hdoscek, M. Muhlhauser, and S. D. Peyerimhoff, Chem. Phys. Lett. 383, 84 (2004). However, we find that the polarity of the solvent influences the excited state energetics, leading to a reversal in the ordering of these two states with 31B1 shifting to lower energies. Molecular dynamics simulations along with linear response and ab initio calculations support the evidence extracted from resonance Raman intensity analysis, providing insights on ClNO2 electronic structure, solvation effects in methanol, and the source of broadening, emphasizing the importance of a contribution from inhomogeneous linewidth. © 2014 AIP Publishing LLC.en
dc.sourceJournal of Chemical Physicsen
dc.subjectChlorine compoundsen
dc.subjectMolecular dynamicsen
dc.subjectElectronic structureen
dc.subjectMolecular dynamics simulationsen
dc.subjectExcited statesen
dc.subjectAb initio calculationsen
dc.subjectElectronic transitionen
dc.subjectRelative contributionen
dc.subjectDepolarization ratioen
dc.subjectDispersion curvesen
dc.subjectExcitation wavelengthen
dc.subjectTransition dipole momentsen
dc.titleAnalysis of depolarization ratios of ClNO2 dissolved in methanolen
dc.description.issue1 Σχολή Θετικών και Εφαρμοσμένων Επιστημών / Faculty of Pure and Applied SciencesΤμήμα Χημείας / Department of Chemistry
dc.contributor.orcidHayes, Sophia C. [0000-0002-2809-6193]

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