TY - JOUR
T1 - Vibrational Dephasing along the Reaction Coordinate of an Electron Transfer Reaction
AU - Yoneda, Yusuke
AU - Kudisch, Bryan
AU - Rafiq, Shahnawaz
AU - Maiuri, Margherita
AU - Nagasawa, Yutaka
AU - Scholes, Gregory D.
AU - Miyasaka, Hiroshi
N1 - Publisher Copyright:
© 2021 American Chemical Society
PY - 2021/9/15
Y1 - 2021/9/15
N2 - The role of molecular vibration in photoinduced electron transfer (ET) reactions has been extensively debated in recent years. In this study, we investigated vibrational wavepacket dynamics in a model ET system consisting of an organic dye molecule as an electron acceptor dissolved in various electron donating solvents. By using broad band pump-probe (BBPP) spectroscopy with visible laser pulses of sub-10 fs duration, coherent vibrational wavepackets of naphthacene dye with frequencies spanning 170-1600 cm-1were observed in the time domain. The coherence properties of 11 vibrational modes were analyzed by an inverse Fourier filtering procedure, and we discovered that the dephasing times of some vibrational coherences are reduced with increasing ET rates. Density functional theory calculations indicated that the corresponding vibrational modes have a large Huang-Rhys factor between the reactant and the product states, supporting the hypothesis that the loss of phase coherence along certain vibrational modes elucidates that those vibrations are coupled to the reaction coordinate of an ET reaction.
AB - The role of molecular vibration in photoinduced electron transfer (ET) reactions has been extensively debated in recent years. In this study, we investigated vibrational wavepacket dynamics in a model ET system consisting of an organic dye molecule as an electron acceptor dissolved in various electron donating solvents. By using broad band pump-probe (BBPP) spectroscopy with visible laser pulses of sub-10 fs duration, coherent vibrational wavepackets of naphthacene dye with frequencies spanning 170-1600 cm-1were observed in the time domain. The coherence properties of 11 vibrational modes were analyzed by an inverse Fourier filtering procedure, and we discovered that the dephasing times of some vibrational coherences are reduced with increasing ET rates. Density functional theory calculations indicated that the corresponding vibrational modes have a large Huang-Rhys factor between the reactant and the product states, supporting the hypothesis that the loss of phase coherence along certain vibrational modes elucidates that those vibrations are coupled to the reaction coordinate of an ET reaction.
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U2 - 10.1021/jacs.1c01863
DO - 10.1021/jacs.1c01863
M3 - Article
C2 - 34474559
AN - SCOPUS:85114892731
SN - 0002-7863
VL - 143
SP - 14511
EP - 14522
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -