论文标题
用“定向外部电场”操纵双原子分子：原子特性中的线性相关性导致非线性分子响应
Manipulation of Diatomic Molecules with 'Oriented External Electric Fields': Linear Correlations in Atomic Properties Lead to Non-Linear Molecular Responses
论文作者
论文摘要
已证明“定向的外部电场（OEEF）”具有巨大的潜力，可以通过从H2存储到分子机的应用来提供对化学反应，催化和选择性的前所未有的控制。我们报告了一项关于因OEEF引起的分子变化原子起源的理论研究。了解原子和分子特性之间OEEF诱导的耦合的特征是彻底了解强域外部场对分子结构，稳定性和反应性影响的重要一步。我们专注于一组同型（H2，N2，O2，F2和Cl2）和异源 - 二核能（HF，HCL，CO和NO分子）在强烈的外部电场下的原子和杂种（HF，HF，HCl，CO和NO）的特性。结果表明，原子特性（原子电荷和能量和定位指数）与磁场强度有线性相关，但是分子特性（键长，键长，键临界点的电子密度，键长的长度，键长和电子异位化指数）表现出非线性响应对障碍物的响应。特别是，电子密度分布的变化改变了零频表面，原子体积，原子电子种群以及定位/离域指数的形状和位置。在分子水平上，分子静电电位的地形和拓扑经历了巨大变化。外部田地还扰动研究化学键的共价离子离子特征，标志着电场对化合物稳定性和反应性的影响。这些发现在分子中原子量子理论的框架内得到了很好的理解，并在原型分子（例如二式分子）中对这些作用形成了连贯的概念理解。
'Oriented external electric fields (OEEFs)' have been shown to have great potential in being able to provide unprecedented control of chemical reactions, catalysis and selectivity with applications ranging from H2 storage to molecular machines. We report a theoretical study of the atomic origins of molecular changes due to OEEFs; understanding the characteristics of OEEF-induced couplings between atomic and molecular properties is an important step toward comprehensive understanding of the effects of strong external fields on molecular structure, stability, and reactivity. We focus on the atomic and molecular (bond) properties of a set of homo- (H2, N2, O2, F2, and Cl2) and hetero-diatomic (HF, HCl, CO, and NO) molecules under intense external electric fields in the context of quantum theory of atoms in molecules (QTAIM). It is shown that atomic properties (atomic charges and energies, and localization index) correlate linearly with the field strengths, but molecular properties (bond length, electron density at bond critical point, bond length, and electron delocalization index) exhibit non-linear responses to the imposed fields. In particular, the changes in the electron density distribution alter the shapes and locations of the zero-flux surfaces, atomic volumes, atomic electron population, and localization/delocalization indices. At the molecular level, the topography and topology of the molecular electrostatic potential undergo dramatic changes. The external fields also perturb the covalent-polar-ionic characteristic of the studied chemical bonds, hallmarking the impact of electric fields on the stability and reactivity of chemical compounds. The findings are well-rationalized within the framework of the quantum theory of atoms in molecules and form a coherent conceptual understanding of these effects in prototypical molecules such as diatomics.
