Floquet Study of Quantum Control of the Cis–Trans Photoisomerization of Rhodopsin

Journal Article · Fri Feb 09 00:00:00 EST 2018 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.7b01217· OSTI ID:1480246

Videla, Pablo E. ^[1]; Markmann, Andreas ^[1]; Batista, Victor S.  ^[1]

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1. Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, United States; Energy Sciences Institute, Yale University, P.O. Box 27394, West Haven, Connecticut 06516-7394, United States

Understanding how to control reaction dynamics of polyatomic systems by using ultrafast laser technology is a fundamental challenge of great technological interest. Here, we report a Floquet theoretical study of the effect of light-induced potentials on the ultrafast cis–trans photoisomerization dynamics of rhodopsin. The Floquet Hamiltonian involves an empirical 3-state 25-mode model with frequencies and excited-state gradients parametrized to reproduce the rhodopsin electronic vertical excitation energy, the resonance Raman spectrum, and the photoisomerization time and efficiency as probed by ultrafast spectroscopy. We simulate the excited state relaxation dynamics using the time-dependent self-consistent field method, as described by a 3-state 2-mode nuclear wavepacket coupled to a Gaussian ansatz of 23 vibronic modes. We analyze the reaction time and product yield obtained with pulses of various widths and intensity profiles, defining ’dressed states’ where the perturbational effect of the pulses is naturally decoupled along the different reaction channels. We find pulses that delay the excited-state photoisomerization for hundreds of femtoseconds, and we gain insights on the underlying control mechanisms. The reported findings provide understanding of quantum control, particularly valuable for the development of ultrafast optical switches based on visual pigments.

• Research Organization: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
• Sponsoring Organization: USDOE
• OSTI ID: 1480246
• Journal Information: Journal of Chemical Theory and Computation, Vol. 14, Issue 3; ISSN 1549-9618
• Country of Publication: United States
• Language: English