2017
DOI: 10.1021/acs.jpcb.7b02329
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The Primary Photochemistry of Vision Occurs at the Molecular Speed Limit

Abstract: Ultrafast photochemical reactions are initiated by vibronic transitions from the reactant ground state to the excited potential energy surface, directly populating excited-state vibrational modes. The primary photochemical reaction of vision, the isomerization of retinal in the protein rhodopsin, is known to be a vibrationally coherent reaction, but the Franck-Condon factors responsible for initiating the process have been difficult to resolve with conventional time-resolved spectroscopies. Here we employ expe… Show more

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Cited by 49 publications
(102 citation statements)
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References 37 publications
(70 reference statements)
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“…S 1 therefore preserves a strongly reactive CT character, and Figure 3 shows that bond length inversion is complete (BLA <0) along the C5=C6-C7=C8-C9=C10-C11=C12 fragment of the chromophore. Both effects lead in the specific protein environment to a barrierless potential and a rapid downhill progression reaching the CInt within less than 100 fs, in agreement with experiments [31,[93][94][95][96]. In 13C/ASR, after an initial BLA displacement, S 1 and S 2 are degenerate in the 40-80 fs time interval, and the dihedral angles, along the C 13 =C 14 & C 15 =N axes, remain almost planar [86].…”
Section: Theoretical Framework: Potential Energy Surfaces and Cintsupporting
confidence: 84%
“…S 1 therefore preserves a strongly reactive CT character, and Figure 3 shows that bond length inversion is complete (BLA <0) along the C5=C6-C7=C8-C9=C10-C11=C12 fragment of the chromophore. Both effects lead in the specific protein environment to a barrierless potential and a rapid downhill progression reaching the CInt within less than 100 fs, in agreement with experiments [31,[93][94][95][96]. In 13C/ASR, after an initial BLA displacement, S 1 and S 2 are degenerate in the 40-80 fs time interval, and the dihedral angles, along the C 13 =C 14 & C 15 =N axes, remain almost planar [86].…”
Section: Theoretical Framework: Potential Energy Surfaces and Cintsupporting
confidence: 84%
“…Also, an ultrafast decay of the S 1 probability towards the photo-products already at 50 fs 38 is common to all results based on the three-dimensional model. We notice quantitative differences between exact results (black lines) and the two approximations of the metric tensor, i.e., constant (dark-green lines) and diagonal-constant (light-green lines).…”
Section: Analysis Of the Model Based On Quantum Dynamics Simulationsmentioning
confidence: 55%
“…For all these reasons, our study goes beyond previous reports based on two-dimensional and/or empirically determined PES models. [21][22][23]25,38,53,56,57 The analysis of the results focuses on three main aspects of PSB3 captured dynamics:…”
Section: Introductionmentioning
confidence: 99%
“…In this process, a photon is absorbed by a chromophore in a light receptor, which causes photoisomerisation. This change in structure induces a change in the structure of the photoreceptor and the resulting signal transduction pathways that lead to a visual signal [5]. This process is very rapid (< 200 femtoseconds) and has a high yield.…”
Section: Introductionmentioning
confidence: 99%