PMID- 28981285
OWN - NLM
STAT- MEDLINE
DCOM- 20180205
LR  - 20180205
IS  - 1948-7185 (Electronic)
IS  - 1948-7185 (Linking)
VI  - 8
IP  - 20
DP  - 2017 Oct 19
TI  - Impact of Electronic State Mixing on the Photoisomerization Time Scale of the 
      Retinal Chromophore.
PG  - 5222-5227
LID - 10.1021/acs.jpclett.7b02344 [doi]
AB  - Spectral data show that the photoisomerization of retinal protonated Schiff base 
      (rPSB) chromophores occurs on a 100 fs time scale or less in vertebrate 
      rhodopsins, it is several times slower in microbial rhodopsins and it is between 
      one and 2 orders of magnitude slower in solution. These time scale variations 
      have been attributed to specific modifications of the topography of the first 
      excited state potential energy surface of the chromophore. However, it is 
      presently not clear which specific environment effects (e.g., electrostatic, 
      electronic, or steric) are responsible for changing the surface topography. Here, 
      we use QM/MM models and excited state trajectory computations to provide evidence 
      for an increase in electronic mixing between the first and the second excited 
      state of the chromophore when going from vertebrate rhodopsin to the solution 
      environments. Ultimately, we argue that a correlation between the lifetime of the 
      first excited state and electronic mixing between such state and its higher 
      neighbor, may have been exploited to evolve rhodopsins toward faster 
      isomerization and, possibly, light-sensitivity.
FAU - Manathunga, Madushanka
AU  - Manathunga M
AD  - Department of Chemistry, Bowling Green State University , Bowling Green, Ohio 
      43403, United States.
FAU - Yang, Xuchun
AU  - Yang X
AD  - Department of Chemistry, Bowling Green State University , Bowling Green, Ohio 
      43403, United States.
FAU - Orozco-Gonzalez, Yoelvis
AU  - Orozco-Gonzalez Y
AD  - Department of Chemistry, Bowling Green State University , Bowling Green, Ohio 
      43403, United States.
AD  - Institut de Physique et Chimie des Materiaux de Strasbourg, UMR 7504 Universite 
      de Strasbourg-CNRS, F-67034 Strasbourg, France.
FAU - Olivucci, Massimo
AU  - Olivucci M
AUID- ORCID: 0000-0002-8247-209X
AD  - Department of Chemistry, Bowling Green State University , Bowling Green, Ohio 
      43403, United States.
AD  - Dipartimento di Biotecnologie, Chimica e Farmacia, Universita di Siena , via A. 
      Moro 2, I-53100 Siena, Italy.
AD  - Institut de Physique et Chimie des Materiaux de Strasbourg, UMR 7504 Universite 
      de Strasbourg-CNRS, F-67034 Strasbourg, France.
LA  - eng
PT  - Journal Article
DEP - 20171011
PL  - United States
TA  - J Phys Chem Lett
JT  - The journal of physical chemistry letters
JID - 101526034
RN  - 0 (Schiff Bases)
RN  - 9009-81-8 (Rhodopsin)
SB  - IM
MH  - *Isomerism
MH  - Photochemistry
MH  - Quantum Theory
MH  - Retina/*chemistry
MH  - Rhodopsin/*chemistry
MH  - *Schiff Bases
MH  - Static Electricity
EDAT- 2017/10/06 06:00
MHDA- 2018/02/06 06:00
CRDT- 2017/10/06 06:00
PHST- 2017/10/06 06:00 [pubmed]
PHST- 2018/02/06 06:00 [medline]
PHST- 2017/10/06 06:00 [entrez]
AID - 10.1021/acs.jpclett.7b02344 [doi]
PST - ppublish
SO  - J Phys Chem Lett. 2017 Oct 19;8(20):5222-5227. doi: 10.1021/acs.jpclett.7b02344. 
      Epub 2017 Oct 11.