The C5H6NH2+ Protonated Shiff Base: An ab Initio Minimal Model for Retinal Photoisomerization

Abstract

The minimum energy path for photoisomerization of the minimal retinal protonated Shiff base model tZt-penta-3,5-dieniminium cation (cis-C5H6NH2+) is computed using MC−SCF and multireference Moller−Plesset methods. The results show that, upon excitation to the spectroscopic state, this molecule undergoes a barrierless relaxation toward a configuration where the excited and ground states are conically intersecting. The intersection point has a ∼80° twisted central double bond which provides a route for fully efficient nonadiabatic cis → trans isomerization. This mechanism suggests that cis-C5H6NH2+ provides a suitable “ab initio” model for rationalizing the observed “ultrafast” (sub-picosecond) isomerization dynamics of the retinal chromophore in rhodopsin. The detailed analysis of the computed reaction coordinate provides information on the changes in molecular structure and charge distribution along the isomerization path. It is shown that the initial excited state motion is dominated by stretching modes ...