4-硝基-1,3-丁二烯基胺分子的氢键效应

Hydrogen Bonding Effects on Geometrical and Electronic Structures of 4-Nitro-buta-1,3-dienylamine

在从头计算的水平上,利用杂化密度泛函理论研究了溶剂对4-硝基-1,3-丁二烯基胺分子的几何结构、分子内的电荷分布和电荷转移态的能量漂移的影响.在四种极性溶剂中,我们构造了包括氢键作用的超分子结构.分别研究了由极化连续模型模拟的溶剂和溶质分子的长程相互作用,溶剂和溶质分子的氢键作用,以及溶剂和溶质分子的整体作用对分子结构和性质的影响.研究结果表明氢键作用引起了溶质分子结构和性质的较大变化,从而将明显地影响该类分子的非线性光学性质.因此,在模拟溶剂效应时需要考虑氢键作用.

The hybrid density functional theory at ab initio level was applied to study solvent effects on geometrical structures, charge distribution, and solvatochromic shifts of 4-nitro-buta-1,3-dienylamine molecule. The super-molecular structures of the solute and the solvent molecules connected by hydrogen bonding have been constructed for four kinds of polar solvents. The long range interaction simulated by polarizable continuum model, the hydrogen bonding interaction, and the whole interaction between the solute and the medium were separately investigated. The numerical results show that the hydrogen bonding interaction may induce a large variation of the structures and properties of 4-nitro-buta-1,3-dienylamine molecule. As a result, the hydrogen bonding interaction should be considered when one intends to simulate the solvent effects accurately.