Institute of Physical and Theoretical Chemistry, Wrocław University of Technology, Wrocław, Poland.
J Phys Chem A. 2011 May 12;115(18):4691-700. doi: 10.1021/jp110226h. Epub 2011 Apr 14.
We report the partitioning of the interaction-induced static electronic dipole (hyper)polarizabilities for linear hydrogen cyanide complexes into contributions arising from various interaction energy terms. We analyzed the nonadditivities of the studied properties and used these data to predict the electric properties of an infinite chain. The interaction-induced static electric dipole properties and their nonadditivities were analyzed using an approach based on numerical differentiation of the interaction energy components estimated in an external electric field. These were obtained using the hybrid variational-perturbational interaction energy decomposition scheme, augmented with coupled-cluster calculations, with singles, doubles, and noniterative triples. Our results indicate that the interaction-induced dipole moments and polarizabilities are primarily electrostatic in nature; however, the composition of the interaction hyperpolarizabilities is much more complex. The overlap effects substantially quench the contributions due to electrostatic interactions, and therefore, the major components are due to the induction and exchange-induction terms, as well as the intramolecular electron-correlation corrections. A particularly intriguing observation is that the interaction first hyperpolarizability in the studied systems not only is much larger than the corresponding sum of monomer properties, but also has the opposite sign. We show that this effect can be viewed as a direct consequence of hydrogen-bonding interactions that lead to a decrease of the hyperpolarizability of the proton acceptor and an increase of the hyperpolarizability of the proton donor. In the case of the first hyperpolarizability, we also observed the largest nonadditivity of interaction properties (nearly 17%) which further enhances the effects of pairwise interactions.
我们报告了线性氢氰酸复合物中相互作用诱导的静态电子偶极（超）极化率的分配，将其分为来自各种相互作用能项的贡献。我们分析了所研究性质的非加和性，并利用这些数据预测了无限链的电性质。使用基于数值微分的方法分析了相互作用诱导的静态电偶极性质及其非加和性，该方法基于在外部电场中估算的相互作用能分量。这些是通过混合变分-微扰相互作用能量分解方案获得的，并辅以单重态、双重态和非迭代三重态的耦合簇计算。我们的结果表明，相互作用诱导的偶极矩和极化率主要是静电性质的；然而，相互作用超极化率的组成要复杂得多。重叠效应大大抑制了静电相互作用的贡献，因此，主要成分是诱导和交换诱导项，以及分子内电子相关修正。一个特别有趣的观察结果是，在研究体系中，相互作用的第一超极化率不仅远远大于单体性质的相应总和，而且符号相反。我们表明，这种效应可以看作是氢键相互作用的直接结果，导致质子受体的超极化率降低和质子供体的超极化率增加。在第一超极化率的情况下，我们还观察到相互作用性质的最大非加和性（近 17%），这进一步增强了成对相互作用的影响。
