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.
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14 January 2012
Research Article|
January 09 2012
Electronic structure calculations in arbitrary electrostatic environments
Mark A. Watson;
Mark A. Watson
Department of Chemistry and Chemical Biology,
Harvard University
, Cambridge, Massachusetts 02138, USA
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Dmitrij Rappoport;
Dmitrij Rappoport
Department of Chemistry and Chemical Biology,
Harvard University
, Cambridge, Massachusetts 02138, USA
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Elizabeth M. Y. Lee;
Elizabeth M. Y. Lee
a)
Department of Chemistry and Chemical Biology,
Harvard University
, Cambridge, Massachusetts 02138, USA
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Roberto Olivares-Amaya;
Roberto Olivares-Amaya
Department of Chemistry and Chemical Biology,
Harvard University
, Cambridge, Massachusetts 02138, USA
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Alán Aspuru-Guzik
Alán Aspuru-Guzik
b)
Department of Chemistry and Chemical Biology,
Harvard University
, Cambridge, Massachusetts 02138, USA
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a)
Present address: Department of Chemical and Biomolecular Engineering and Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
b)
Electronic mail: aspuru@chemistry.harvard.edu.
J. Chem. Phys. 136, 024101 (2012)
Article history
Received:
November 03 2011
Accepted:
November 28 2011
Citation
Mark A. Watson, Dmitrij Rappoport, Elizabeth M. Y. Lee, Roberto Olivares-Amaya, Alán Aspuru-Guzik; Electronic structure calculations in arbitrary electrostatic environments. J. Chem. Phys. 14 January 2012; 136 (2): 024101. https://doi.org/10.1063/1.3670417
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