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Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Kumar, Venkatraman Ravi and Rajkumar, Nagappan and Umapathy, Siva (2015) Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study. In: JOURNAL OF CHEMICAL PHYSICS, 142 (2).

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Official URL: http://dx.doi.org/ 10.1063/1.4905126


Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-pi(1)*; S-1 state) and the shorter (1 pi-pi(1)*; S-2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S-2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C-2 nu symmetry constraint on the S-2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling. (C) 2015 AIP Publishing LLC.

Item Type: Journal Article
Additional Information: Copy right for this article belongs to the AMER INST PHYSICS, 1305 WALT WHITMAN RD, STE 300, MELVILLE, NY 11747-4501 USA
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 04 Mar 2015 11:58
Last Modified: 04 Mar 2015 11:58
URI: http://eprints.iisc.ac.in/id/eprint/50945

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