title: Electronic structure calculations in arbitrary electrostatic environments.
abstract: 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.
authors.affiliation: Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Watson
authors.forename: Dmitrij
authors.initials: D
authors.lastname: Rappoport
authors.forename: Elizabeth M Y
authors.initials: EM
authors.lastname: Lee
authors.forename: Roberto
authors.initials: R
authors.lastname: Olivares-Amaya
authors.forename: Alán
authors.initials: A
authors.lastname: Aspuru-Guzik
mesh_terms: D001554:Benzene / Q000737:chemistry; D004583:Electrons; D005998:Glycine / Q000737:chemistry; D008670:Metals / Q000737:chemistry; D015394:Molecular Structure; D049329:Nanostructures / Q000737:chemistry; D011789:Quantum Theory; D055672:Static Electricity; D013499:Surface Properties
chemical_list: D008670:Metals; D001554:Benzene; D005998:Glycine