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Title: The cavity electromagnetic field within the polarizable continuum model of solvation

Cavity field effects can be defined as the consequences of the solvent polarization induced by the probing electromagnetic field upon spectroscopies of molecules in solution, and enter in the definitions of solute response properties. The polarizable continuum model of solvation (PCM) has been extended in the past years to address the cavity-field issue through the definition of an effective dipole moment that couples to the external electromagnetic field. We present here a rigorous derivation of such cavity-field treatment within the PCM starting from the general radiation-matter Hamiltonian within inhomogeneous dielectrics and recasting the interaction term to a dipolar form within the long wavelength approximation. To this aim we generalize the Göppert-Mayer and Power-Zienau-Woolley gauge transformations, usually applied in vacuo, to the case of a cavity vector potential. Our derivation also allows extending the cavity-field correction in the long-wavelength limit to the velocity gauge through the definition of an effective linear momentum operator. Furthermore, this work sets the basis for the general PCM treatment of the electromagnetic cavity field, capable to describe the radiation-matter interaction in dielectric media beyond the long-wavelength limit, providing also a tool to investigate spectroscopic properties of more complex systems such as molecules close to large nanoparticles.
Authors:
 [1] ;  [2] ;  [1] ;  [3]
  1. Center S3, CNR Institute of Nanoscience, Modena (Italy)
  2. (Italy)
  3. Department of Chemistry, UniversitĂ  degli studi di Parma, Parma (Italy)
Publication Date:
OSTI Identifier:
22252981
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DIELECTRIC MATERIALS; DIPOLE MOMENTS; ELECTROMAGNETIC FIELDS; GAUGE INVARIANCE; HAMILTONIANS; INTERACTIONS; LINEAR MOMENTUM OPERATORS; NANOSTRUCTURES; PARTICLES; POLARIZATION; SOLUTES; SOLUTIONS; SOLVATION; SOLVENTS; SPECTROSCOPY; WAVELENGTHS