对几种共轭分子中原子共面问题的浅析

借助文献和互联网资料,对共价键的自由旋转作出了界定。分析了1,3-丁二烯和联苯等几种共轭分子的碳碳单键旋转及原子共面问题,认为单键能否旋转与分子的旋转能垒及温度等外界条件有关。常温下,1,3-丁二烯分子中的原子不是都在同一平面上;联苯在固态时,分子中的22个原子都在同一平面,而在液态或气态时,两个苯环间出现了0°～45°之间的扭转二面角,分子中只有14个原子在同一平面上。

Effects of Rotational Isomerism and Bond Length Alternation on Optical Spectra of FTC Chromophore in Solution

Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.

过渡态理论在化学体系中的2个应用实例

在大学本科一二年级的物理化学教学中,化学动力学章节的学习涉及到对不同时间尺度的认识。本文利用过渡态理论得到的速率常数表达公式,以乙烷分子碳/碳单键旋转和水分子氢键交换的动力学过程为例,对这2个应用实例的动力学过程所发生的时间尺度做出估算。这些时间尺度的估算对于学生理解不同动力学过程的物理图像至关重要,同时也有助于加强学生对重要公式的理解并能够将这些公式在化学体系中灵活运用。