Using 1,3‐butadiene and 1,3,5‐hexatriene to model the cis‐trans isomerization of retinal, the chromophore in the visual pigment rhodopsin

Abstract

AbstractThe short polyenes 1,3‐butadiene and 1,3,5‐hexatriene are used to model the cis‐trans isomerization of the protonated Schiff base of retinal (PSBR) in rhodopsin (Rh). We employed the complete active space self‐consistent field (CASSCF) method for calculation of the potential energy surfaces (PESs) in C2 symmetry. In the calculations, the central bond was twisted from 0 to 180° in the first singly excited singlet state (Sse), i.e., the state dominated by a configuration with one electron excited from HOMO to LUMO. It was found that the PES of 1,3‐butadiene has a maximum whereas the PES of 1,3,5‐hexatriene has a minimum for a twist angle of 90°. This is explained by a shift in border of single and double bonds in the Sse state. The first step in the cis‐trans isomerization of PSBR, which is the formation of the C6C7 (see Scheme 1 for numbering) twisted PSBR in the first excited singlet state (S1), inside the protein binding pocket of the visual pigment Rh is modeled using crystal coordinates and the calculations performed on 1,3‐butadiene and 1,3,5‐hexatriene. More specifically, a plausible approximate structure is calculated in a geometric way for the C6C7 90° twisted PSBR, which fits into the protein binding pocket in the best possible way. It has been shown earlier that PSBR has an energy minimum for this angle in S1. The CASSCF method was used to investigate the wave function of the calculated structure of PSBR. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002