TIME-DEPENDENT DENSITY FUNCTIONAL THEORY STUDY ON THE ELECTRONIC EXCITED-STATE HYDROGEN BONDING DYNAMICS OF METHYL ACETATE IN AQUEOUS SOLUTION

摘要

The time-dependent density functional theory (TDDFT) method has been carried out to investigate the hydrogen-bonding dynamics of methyl acetate (CH3 CO2CH3) 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 CH3CO2CH3 and H2O monomers, the hydrogen-bonded CH3CO2CH3-(H2O)1, 2 complexes have been calculated using DFT and TDDFT methods respectively. One intermolecular hydrogen bond C=O⋯H–O is formed between CH3CO2CH3 and one water molecule in CH3CO2CH3-H2O dimer. Meanwhile, in CH3CO2CH3-(H2O)2 trimer, two intermolecular hydrogen bonds C=O⋯H–O are formed between CH3CO2CH3 and two water molecules. By theoretically monitoring the excitation energy changes among the CH3CO2CH3 monomer, the CH3CO2CH3-H2O dimer, and the CH3CO2CH3-(H2O)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 CH3CO2CH3-(H2O)1, 2 complexes.