Photoisomerization Path for a Realistic Retinal Chromophore Model:  The Nonatetraeniminium Cation

Photoisomerization Path for a Realistic Retinal Chromophore Model:  The Nonatetraeniminium Cation

In this paper, ab initio CASSCF computations are used to investigate the photoisomerization path of the protonated Schiff base (PSB) 4-cis-γ-methylnona-2,4,6,8-tetraeniminium cation:  a five conjugated double bond model of the retinal chromophore of rhodopsin (the human retina visual pigment).We sho...

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Veröffentlicht in:Journal of the American Chemical Society 1998-02, Vol.120 (6), p.1285-1288
Hauptverfasser: Garavelli, Marco, Vreven, Thom, Celani, Paolo, Bernardi, Fernando, Robb, Michael A, Olivucci, Massimo
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container_issue 6
container_start_page 1285
container_title Journal of the American Chemical Society
container_volume 120
creator Garavelli, Marco
Vreven, Thom
Celani, Paolo
Bernardi, Fernando
Robb, Michael A
Olivucci, Massimo
description In this paper, ab initio CASSCF computations are used to investigate the photoisomerization path of the protonated Schiff base (PSB) 4-cis-γ-methylnona-2,4,6,8-tetraeniminium cation:  a five conjugated double bond model of the retinal chromophore of rhodopsin (the human retina visual pigment).We show that, after initial skeletal relaxation from the Franck−Condon region (which involves a large increase in the central CC bond length), the system is “trapped” in an energy plateau on the S1 energy surface which may be the origin of the “slow” cis → trans isomerization dynamics observed in retinal PSBs in solution. The energy plateau is absent in shorter retinal chromophore models which have a steeper S1 isomerization path. The rhodopsin cavity (where the native chromophore is embedded) may have the effect of removing the energy plateau from the S1 potential thus dramatically increasing the photoisomerization rate from picoseconds to femtoseconds.
doi_str_mv 10.1021/ja972695i
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title Photoisomerization Path for a Realistic Retinal Chromophore Model:  The Nonatetraeniminium Cation
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