Watson, Mark A.Rappoport, DmitrijLee, Elizabeth M. Y.Olivares-Amaya, RobertoAspuru-Guzik, Alan2012-03-142012Watson, Mark A., Dmitrij Rappoport, Elizabeth M. Y. Lee, Roberto Olivares-Amaya, and Alán Aspuru-Guzik. 2012. Electronic Structure Calculations in Arbitrary Electrostatic Environment. Journal of Chemical Physics 136(2): 024101.0021-96061089-7690http://nrs.harvard.edu/urn-3:HUL.InstRepos:8366165Modeling 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.en-USdensity functional theorymolecular electronic statesJournal Article2012-03-1410.1063/1.3670417