Time-dependent density functional theory study on the electronic excited-state hydrogen bonding dynamics of methyl acetate in aqueous solution

The time-dependent density functional theory (TDDFT) method has been carried out to investigate the hydrogen-bonding dynamics of methyl acetate (CH(3)CO(2)CH(3)) in hydrogen-donating water solvent. The ground-state geometry optimizations, electronic transition energies and corresponding oscillation strengths of the low-lying electronically-excited states for the isolated CH(3)CO(2)CH(3) and H(2)O monomers, the hydrogen-bonded CH(3)CO(2)CH(3)-(H(2)O)(1,2) complexes have been calculated using DFT and TDDFT methods respectively. One intermolecular hydrogen bond C=O center dot center dot center dot H-O is formed between CH(3)CO(2)CH(3) and one water molecule in CH(3)CO(2)CH(3)-H(2)O dimer. Meanwhile, in CH(3)CO(2)CH(3)-(H(2)O)(2) trimer, two intermolecular hydrogen bonds C=O center dot center dot center dot H-O are formed between CH(3)CO(2)CH(3) and two water molecules. By theoretically monitoring the excitation energy changes among the CH(3)CO(2)CH(3) monomer, the CH(3)CO(2)CH(3)-H(2)O dimer, and the CH(3)CO(2)CH(3)-(H(2)O)(2) trimer, we have demonstrated interestingly that in some electronically-excited states, the intermolecular hydrogen bonds are strengthened inducing electronic spectral redshifts, while in others weakened with electronic spectral blueshifts. The phenomenon that hydrogen bonds are strengthened in some electronic states while weakened in others can arouse further probe into CH(3)CO(2)CH(3)-(H(2)O)(1,2) complexes.