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Title: Solvent-mediated internal conversion in diphenoxyethane-(H{sub 2}O){sub n}clusters, n = 2-4

1,2-diphenoxyethane (DPOE) is a flexible bichromophore whose excited states come in close-lying pairs whose splitting and vibronic coupling can be modulated by solvent. Building on the ground state infrared spectroscopy of DPOE-(H{sub 2}O){sub n} clusters with n = 2-4 from the adjoining paper [Walsh et al., J. Chem. Phys. 142, 154303 (2015)], the present work focuses on the vibronic and excited state infrared spectroscopies of the clusters. The type and degree of asymmetry of the water cluster binding to DPOE is reflected in the variation in the magnitude of the S{sub 1}/S{sub 2} splitting with cluster size. Excited state resonant ion-dip infrared spectroscopy was performed at the electronic origins of the first two excited states in order to explore how the water clusters’ OH stretch spectra report on the nature of the two excited states, and the interaction of the S{sub 2} state with nearby S{sub 1} vibronic levels mediated by the water clusters. The data set, when taken as a whole, provides a state-to-state view of internal conversion and the role of solvent in mediating conversion of electronic excitation between two chromophores, providing a molecular-scale view of Kasha’s rule.
Authors:
; ; ;  [1]
  1. Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084 (United States)
Publication Date:
OSTI Identifier:
22415673
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; COUPLING; ETHANE; EXCITATION; EXCITED STATES; GROUND STATES; INFRARED SPECTRA; INTERNAL CONVERSION; MOLECULAR CLUSTERS; SOLVENTS; VARIATIONS; WATER