A quantum mechanical/molecular dynamics/mean field study of acrolein in aqueous solution: Analysis of H bonding and bulk effects on spectroscopic properties

A novel molecular dynamics methodology recently proposed by our group [Rega , Chem. Phys. Lett. 422, 367 (2006)], which is based on an integrated hybrid potential rooted in high level quantum mechanical methods using localized basis functions and nonperiodic boundary conditions, has been applied to study acrolein in aqueous solution. The solute structural rearrangement and its hydrogen-bonding pattern due to the interactions with water have been analyzed in some detail. Moreover, the solvent effects on the UV n ->pi* vertical transition and on the NMR C-13 and O-17 shielding constants of acrolein have been investigated theoretically by performing a posteriori quantum mechanical calculations on a statistically significant number of snapshots extracted from both gas-phase and aqueous solution simulations. Results show that such effective computational strategy can be successfully used to improve our understanding, at atomic level, of important spectroscopic observables. (c) 2006 American Institute of Physics.