TY - JOUR
T1 - Retinal chromophore photoinduced molecular motion and reactivity
T2 - Isolated conditions and counterion effects
AU - Garavelli, Marco
AU - Bernardi, Fernando
AU - Cembran, Alessandro
AU - Olivucci, Massimo
PY - 2002/1/1
Y1 - 2002/1/1
N2 - Recent, work in the field of biological photoreceptors has demonstrated that computational chemistry can be successfully applied to ultrafast photobiological problems. Here we revise the results of the photoisomerization path mapping of the protonated Schiff base of retinal: the chromophore of rhodopsin proteins. These studies have produced the two-state/two-mode model which provides a rationale for the photon-induced molecular motion in the isolated retinal chromophore. Such model represents a substantial revision of the previous models for the primary event in vision in animals and light driven proton-pumping in halobacteriae. New computational results will be presented, which model the effects of an external counterfoil on the photoisomerization paths. Energetic, electronic, stereoselectivity control and tuning-effects will be analyzed and discussed in terms of counterfoil positions. Both solution and protein experimental data are revised using the new reactivity model.
AB - Recent, work in the field of biological photoreceptors has demonstrated that computational chemistry can be successfully applied to ultrafast photobiological problems. Here we revise the results of the photoisomerization path mapping of the protonated Schiff base of retinal: the chromophore of rhodopsin proteins. These studies have produced the two-state/two-mode model which provides a rationale for the photon-induced molecular motion in the isolated retinal chromophore. Such model represents a substantial revision of the previous models for the primary event in vision in animals and light driven proton-pumping in halobacteriae. New computational results will be presented, which model the effects of an external counterfoil on the photoisomerization paths. Energetic, electronic, stereoselectivity control and tuning-effects will be analyzed and discussed in terms of counterfoil positions. Both solution and protein experimental data are revised using the new reactivity model.
KW - Ab-Initio
KW - CASPT2
KW - CASSCF
KW - Computational Photochemistry
KW - Photoisomerization
KW - Protonated Schiff Bases
KW - Retinal
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U2 - 10.3233/JCM-2002-23-419
DO - 10.3233/JCM-2002-23-419
M3 - Article
AN - SCOPUS:84948987015
VL - 2
SP - 431
EP - 439
JO - Journal of Computational Methods in Sciences and Engineering
JF - Journal of Computational Methods in Sciences and Engineering
SN - 1472-7978
IS - 3-4
ER -