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EXCITED STATE DYNAMICS OF RETINAL PROTEINS AS STUDIED BY FOURIER TRANSFORM OF OPTICAL ABSORPTION SPECTRUM—II. THEORETICAL ANALYSIS OF WAVEPACKET PROPAGATION OF RHODOPSIN
Author(s) -
Kakitani Toshiaki,
Matsuda Narifumi,
Hatano Yasuyo,
Shichida Yoshinori,
Kakitani Hiroko
Publication year - 1992
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1992.tb09721.x
Subject(s) - excited state , fourier transform , chemistry , relaxation (psychology) , wave packet , absorption spectroscopy , absorption (acoustics) , resonance (particle physics) , atomic physics , observable , harmonic oscillator , rhodopsin , raman spectroscopy , molecular physics , physics , retinal , optics , quantum mechanics , psychology , social psychology , biochemistry
Abstract— We theoretically calculated the absolute value of the time correlation function (tcf) of the wavepacket propagation in the excited state using the independent harmonic oscillators model for vibration and compared it with the experimental data obtained by the Fourier transform of optical absorption spectrum (FTOA) of rhodopsin in the preceding paper. We found that the theoretically calculated tcf differs significantly from the FTOA data. This fact indicates that the intrinsic harmonic oscillators model is too crude. We showed that better agreement is obtained between the calculated tcf and the FTOA data if we add an extra mode with low frequency and considerable decay constant which is not observable in the resonance Raman spectra. We also proposed that substantial mode‐mixing would take place among normal coordinates of vibrations at the Franck‐Condon state of the excited state and would contribute to the very rapid relaxation of vibrational energies.