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Excited-State Vibronic Dynamics of Bacteriorhodopsin from Two-Dimensional Electronic Photon Echo Spectroscopy and Multiconfigurational Quantum Chemistry

authors
Samer Gozem, Philip J. M. Johnson, Alexei Halpin, Hoi Ling Luk, Takefumi Morizumi, Valentyn I. Prokhorenko, Oliver P. Ernst, Massimo Olivucci, and R. J. Dwayne Miller.
date published
April 24, 2020
journal
J. Phys. Chem. Lett
volume, number
11
pages
3889-3896
web page
https://pubs.acs.org/doi/10.1021/acs.jpclett.0c01063
doi
https://doi.org/10.1021/acs.jpclett.0c01063
abstract

Owing to the ultrafast time scale of the photoinduced reaction and high degree of spectral overlap among the reactant, product, and excited electronic states in bacteriorhodopsin (bR), it has been a challenge for traditional spectroscopies to resolve the interplay between vibrational dynamics and electronic processes occurring in the retinal chromophore of bR. Here, we employ ultrafast two-dimensional electronic photon echo spectroscopy to follow the early excited-state dynamics of bR preceding the isomerization. We detect an early periodic photoinduced absorptive signal that, employing a hybrid multiconfigurational quantum/molecular mechanical model of bR, we attribute to periodic mixing of the first and second electronic excited states (S1 and S2, respectively). This recurrent interaction between S1 and S2, induced by a bond length alternation of the retinal chromohore, supports the hypothesis that the ultrafast photoisomerization in bR is initiated by a process involving coupled nuclear and electronic motion on three different electronic