Calaminici Patrizia, Jug Karl, Köster Andreas M, Arbez-Gindre Cécile, Screttas Constantinos G
Theoretische Chemie, Universität Hannover, Germany.
J Comput Chem. 2002 Jan 30;23(2):291-7. doi: 10.1002/jcc.10006.
This paper presents calculations of dipole moments (mu), static polarizabilities (alpha), and first hyperpolarizabilities (beta) of phosphonic acid stilbene derivatives calculated in the framework of density functional theory. These calculations were performed using a finite field approach implemented in the density functional program ALLCHEM and were of an all-electron type using local exchange-correlation functional and specially designed basis sets. The molecular structures have been fully optimized using the semiempirical program MSINDO. Some of the investigated stilbenes have been synthesized very recently while others are described for the first time. Donor and acceptor groups of these analogues have been modified and the influence of these changes on the first hyperpolarizabilities has been investigated. This work demonstrates that the nonlinear optical response beta of these compounds increases dramatically when the acceptor moiety is displaced by analogues containing alkali metal groups. A general mechanism for the design of novel nonlinear optical materials with large first hyperpolarizabilities is described.
本文介绍了在密度泛函理论框架下计算的膦酸芪衍生物的偶极矩（μ）、静态极化率（α）和第一超极化率（β）。这些计算使用了密度泛函程序ALLCHEM中实现的有限场方法，并且是全电子类型的，采用了局域交换相关泛函和专门设计的基组。分子结构已使用半经验程序MSINDO进行了完全优化。一些被研究的芪类化合物是最近才合成的，而其他一些则是首次被描述。这些类似物的供体和受体基团已经被修饰，并且研究了这些变化对第一超极化率的影响。这项工作表明，当受体部分被含碱金属基团的类似物取代时，这些化合物的非线性光学响应β会急剧增加。描述了一种设计具有大第一超极化率的新型非线性光学材料的一般机制。
