Time-dependent Density Functional Theory Study on the Electronically Excited States of N-Methylformamide in Aqueous Solution

• 作者: GUO Ming-Xing HAN Yi-Xuan HE Xiang-Yi MA Chao SONG Zhe XU Xue-Song YIN Shu-Hui
• 来源期刊: 结构化学
• 学科: 化学
• 关键词: 密度泛函理论 电子激发态 甲基甲酰胺 水溶液 时间依赖 分子间氢键 TDDFT 优化计算
• 年，卷（期）: 2012,（7）
• 页码范围: 925-932
• 页数: 8页
• 分类号: O641.121|O561.4
• 语种: 英文

摘要

Excited-state hydrogen-bonding dynamics of N-methylformamide （NMF） in water has been investigated by time-dependent density functional theory （TDDFT） method. The ground-state geometry optimizations were calculated by density functional theory （DFT） method, while the electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states of isolated NMF, water monomers and the hydrogen-bonded NMF-H 2 O were calculated by TDDFT method. According to Zhao＇s rule on the excited-state hydrogen bonding dynamics, our results demonstrate that the intermolecular hydrogen bond C=O···O-H is strengthened and weakened in different electronically excited states. The hydrogen bond strengthening and weakening in the electronically excited state plays an important role in the photophysics of NMF in solutions.