Retinal models: comparison of electronic absorption spectra in the gas phase and in methanol solution.
An accurate study on several models of the 11-cis-retinal protonated Schiff base (PSB) has been performed both in vacuo and in methanol solution. Condensed phase calculations have been carried out making use of the ASEP/MD method, which permits the employment of the same high-level ab initio calculations usually applied in gas phase studies as well as a detailed description of the solvent structure around the solute through molecular dynamics simulations of the complete system. The solute structure was completely optimized in vacuo and in solution at the CASSCF level and/or MP2 level, and the CASPT2 method was applied for the calculation of the vertical transition energies and solvent shift values. Our results reproduce and explain the main features of the experimental absorption spectra of the 11-cis-retinal PSB. Two well-resolved bands can be identified in vacuo (separated by roughly 1.0 eV), whereas only a single broad band is observed in solution. This fact is explained by the existence of two almost degenerate excited states in methanol. The inclusion of two methyl groups at the iminium end of the system permits the reproduction of the experimental solvent shift value.
Muñoz-Losa
Aurora
A
Química Física, Universidad de Extremadura, Avenida de Elvas s/n, 06071 Badajoz, Spain.
Fdez Galván
Ignacio
I
Aguilar
Manuel A
MA
Martín
M Elena
ME
D000465:Algorithms; D003198:Computer Simulation; D005740:Gases; D000432:Methanol / Q000737:chemistry*; D008958:Models, Molecular; D011789:Quantum Theory; D012172:Retinaldehyde / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D012997:Solvents / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet / Q000379:methods*; D013237:Stereoisomerism; D013816:Thermodynamics
D005740:Gases; D012996:Solutions; D012997:Solvents; D012172:Retinaldehyde; D000432:Methanol