Probing the Interstate Coupling near a Conical Intersection by Optical Spectroscopy

Farag, Marwa H.; Jansen, Thomas L. C.; Knoester, Jasper

doi:10.1021/acs.jpclett.6b01463

Cited by 27 publications

(32 citation statements)

References 72 publications

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“…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%

Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model

Marsili

Olivucci

Lauvergnat

et al. 2020

J. Chem. Theory Comput.

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We report an in-depth analysis of the photo-induced isomerization of the 2-cispenta-2,4-dieniminium cation: a minimal model of the 11-cis retinal protonated Schiff base chromophore of the dim-light photoreceptor rhodopsin. Based on recently-developed three-dimensional potentials parametrized on ab initio multi-state multi-configurational second-order perturbation theory data, we perform quantum-dynamical studies. In addition, simulations based on various quantum-classical methods, among which Tully surface hopping and the coupled-trajectory approach derived from the exact factorization, allow us to validate their performance against vibronic-wavepacket propagation and, therefore, a purely quantum treatment. Quantum-dynamics results uncover qualitative differences with respect to the two-dimensional Hahn-Stock potentials, widely-used as model potentials for the isomerization of the same chromophore, due to the increased dimensionality and three-mode correlation. Quantum-classical simulations show, instead, that three-dimensional model potentials are capable of capturing a number of features revealed by atomistic simulations and experimental observations. In particular, a recently reported vibrational phase relationship between double-bond torsion and hydrogen-out-of-plane modes critical for rhodopsin isomerization efficiency is correctly reproduced.

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Section: Introductionmentioning

confidence: 99%

Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model

Marsili

Olivucci

Lauvergnat

et al. 2020

J. Chem. Theory Comput.

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“…Conical intersections [1][2][3][4][5][6][7][8] are points or seams of degeneracy between potential energy surfaces (PESs). Conical intersections play major roles in photochemical reactions and ultrafast radiationless decays, such as carotenoid S 2 -S 1 , [9][10][11] DNA bases, [12][13][14][15] cyanine dyes, 1,16 and rhodopsin isomerization.…”

Section: Introductionmentioning

confidence: 99%

Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

Arsenault

et al. 2019

Phys. Chem. Chem. Phys.

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“…In addition, it has been proposed to use vibrational coherence in 2D spectra to measure the interstate coupling near a CI. 28 Also attosecond spectroscopy has been proposed to use to detect the CI by monitoring the electronic coherence at the degenerate point between the adjacent PESs. 29 More recently, a numerical calculation has shown that photorelaxation in uracil can be fully modulated to form the long-lived excited state by a properly shaped laser pulse.…”

Section: Introductionmentioning

confidence: 99%

Tracking an electronic wave packet in the vicinity of a conical intersection

Duan

Sun

et al. 2017

The Journal of Chemical Physics

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This work treats the impact of vibrational coherence on the quantum efficiency of a dissipative electronic wave packet in the vicinity of a conical intersection by monitoring the time-dependent wave packet projection onto the tuning and the coupling mode. The vibrational coherence of the wave packet is tuned by varying the strength of the dissipative vibrational coupling of the tuning and the coupling modes to their thermal baths. We observe that the most coherent wave packet yields a quantum efficiency of 93%, but with a large transfer time constant. The quantum yield is dramatically decreased to 50% for a strongly damped incoherent wave packet, but the associated transfer time of the strongly localized wave packet is short. In addition, we find for the strongly damped wave packet that the transfer occurs via tunneling of the wave packet between the potential energy surfaces before the seam of the conical intersection is reached and a direct passage takes over. Our results provide direct evidence that vibrational coherence of the electronic wave packet is a decisive factor which determines the dynamical behavior of a wave packet in the vicinity of the conical intersection.

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Probing the Interstate Coupling near a Conical Intersection by Optical Spectroscopy

Cited by 27 publications

References 72 publications

Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model

Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model

Two-dimensional electronic-vibrational spectroscopic study of conical intersection dynamics: an experimental and electronic structure study

Tracking an electronic wave packet in the vicinity of a conical intersection

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