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Transient vibrational temperatures estimated from anti‐Stokes and Stokes Raman intensities and vibrational cooling of electronically excited trans ‐stilbene in solution
Author(s) -
Okamoto Hiromi,
Nakabayashi Takakazu,
Tasumi Mitsuo
Publication year - 2000
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/(sici)1097-4555(200004)31:4<305::aid-jrs543>3.0.co;2-0
Subject(s) - photoexcitation , raman spectroscopy , chemistry , intermolecular force , transient (computer programming) , vibrational energy , hot band , coherent anti stokes raman spectroscopy , excitation , analytical chemistry (journal) , raman scattering , molecular vibration , atomic physics , molecular physics , excited state , molecule , optics , physics , organic chemistry , chromatography , computer science , operating system , quantum mechanics
To examine vibrational cooling of trans ‐stilbene in the S 1 state, transient temperatures of a few vibrational modes were estimated by analyzing transient anti‐Stokes and Stokes Raman intensities. Vibrational temperatures obtained for the olefinic C = C and C–Ph stretches are 900 and 680 K, respectively, at 0 ps after photoexcitation (temporal resolution ca 5 ps). These values are higher than the equilibrium temperature (ca 550 K) calculated for a statistical distribution of excess vibrational energy. Ultrafast intermolecular energy flow (vibrational cooling) is discussed based on a model analysis. Copyright © 2000 John Wiley & Sons, Ltd.