Time-Dependent Density Functional Theory Study on Excited-State Hydrogen Bonding Dynamics of Acetic Acid Hydrates |
| |
Authors: | Mingxian Ma Dapeng Yang |
| |
Institution: | (1) Physics Laboratory, North China University of Water Resources and Electric Power, Zhengzhou, 450011, People’s Republic of China;(2) Environmental Science and Engineering College, Dalian Maritime University, Dalian, 116026, Liaoning, People’s Republic of China;(3) Department of Environmental Engineering, University Southern California, Los Angeles, CA, USA; |
| |
Abstract: | The time-dependent density functional theory (TDDFT) method was performed to investigate the hydrogen-bonding dynamics of
acetic acid (AA) hydrates in aqueous solution. For AA, it tends to be both active hydrogen acceptor and donor and denote double
H-bonds as OA···HW and HA···OW, resulting in ring structure hydrates. The ground-state geometry optimizations and electronic transition energies and corresponding
oscillation strengths of the low-lying electronically excited states for the isolated AA monomer and the hydrogen-bonded ring
structure hydrates are calculated by the density functional theory and TDDFT methods, respectively. Different types of intermolecular
hydrogen bonds are formed between one AA molecule and water molecules. According to Zhao’s rule on the excited-state hydrogen
bonding dynamics, it can be found that the intermolecular hydrogen bonds OA···HW and HA···OW are strengthened in electronically excited states of the hydrogen-bonded ring structure hydrates, with the excitation energy
of a related excited state being lowered and electronic spectral redshifts being induced. Moreover, the hydrogen bond strengthening
in the electronically excited state is crucial to the photophysics and photochemistry of hydrates with AA in aqueous solution. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|