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Effects of water re-location and cavity trimming on the CASPT2//CASSCF/AMBER excitation energy of Rhodopsin

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Abstract

We have used quantum-mechanics/molecular-mechanics computations based on ab initio multiconfigurational perturbation theory to determine and rationalize the effect of the re-location of one crystallographic water molecule on the vertical excitation energy of the visual pigment rhodopsin. It is found that the re-location of one water molecule to the opposite side of the 11-cis retinal chromophore leads to a large 0.7–0.8 Å contraction in the chromophore—counterion salt-bridge distance. In spite of this structural effect, the change in excitation energy is found to be limited (< 1.5 kcal mol−1). Through an analysis of different rhodopsin models in terms of “components” (isolated chromophore, isolated chromophore—counterion ion-pair and models deprived of the counterion charges) we show that the limited change of the excitation energy can be related to a displacement of the retinal chromophore to a different spot of the protein cavity.

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Authors and Affiliations

  1. Dipartimento di Chimica, Università di Siena, via Aldo Moro 2, 53100, Siena, Italy

    Angela Strambi, Pedro B. Coto & Massimo Olivucci

  2. Laboratoire de Chimie Théorique et de Modélisation Moléculaire, UMR 6517- CNRS Université de Provence, Case 521, Faculté de Saint-Jérôme, Av. Esc. Normandie Niemen, 13397, Marseille Cedex 20, France

    Nicolas Ferré

  3. Chemistry Department, Bowling Green State University, Bowling Green, OH, 43403, USA

    Massimo Olivucci

Authors
  1. Angela Strambi
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  2. Pedro B. Coto
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  3. Nicolas Ferré
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  4. Massimo Olivucci
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Correspondence to Massimo Olivucci.

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Contribution to the Fernando Bernardi Memorial Issue.

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Strambi, A., Coto, P.B., Ferré, N. et al. Effects of water re-location and cavity trimming on the CASPT2//CASSCF/AMBER excitation energy of Rhodopsin. Theor Chem Account 118, 185–191 (2007). https://doi.org/10.1007/s00214-007-0273-y

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  • DOI: https://doi.org/10.1007/s00214-007-0273-y

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