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Origin of the bathochromic shift in the early photointermediates of the rhodopsin visual cycle: A CASSCF/CASPT2 study



CASSCF/CASPT2 calculations have been applied to study the excited-state properties of the chromophore in rhodopsin and in the early photointermediate, photorhodopsin. For rhodopsin, the chromophore geometry was taken from an optimized X-ray structure while for photorhodopsin the structure proposed by Bifone et al.J Phys Chem B 1997, 101, 2954 was employed. The experimentally observed bathochromic shift of 72 nm is faithfully reproduced by the calculation. Analysis of a model chromophore in which the transition between the geometries is performed stepwise reveals that this shift is predominantly caused by double bond torsion. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003