Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
J Chem Phys. 2012 Jan 14;136(2):024101. doi: 10.1063/1.3670417.
Modeling of electronic structure of molecules in electrostatic environments is of considerable relevance for surface-enhanced spectroscopy and molecular electronics. We have developed and implemented a novel approach to the molecular electronic structure in arbitrary electrostatic environments that is compatible with standard quantum chemical methods and can be applied to medium-sized and large molecules. The scheme denoted CheESE (chemistry in electrostatic environments) is based on the description of molecular electronic structure subject to a boundary condition on the system/environment interface. Thus, it is particularly suited to study molecules on metallic surfaces. The proposed model is capable of describing both electrostatic effects near nanostructured metallic surfaces and image-charge effects. We present an implementation of the CheESE model as a library module and show example applications to neutral and negatively charged molecules.
在静电环境中对分子的电子结构进行建模对于表面增强光谱学和分子电子学具有重要意义。我们已经开发并实现了一种新的方法，可以在任意静电环境中研究分子的电子结构，该方法与标准量子化学方法兼容，并可应用于中大型分子。该方案被称为 CheESE（静电环境中的化学），它基于对分子电子结构的描述，并在系统/环境界面上施加边界条件。因此，它特别适合研究金属表面上的分子。所提出的模型能够描述纳米结构金属表面附近的静电效应和像电荷效应。我们提出了 CheESE 模型的实现作为库模块，并展示了对中性和带负电荷分子的应用示例。
