title: Raman scattering mediated by neighboring molecules.
abstract: Raman scattering is most commonly associated with a change in vibrational state within individual molecules, the corresponding frequency shift in the scattered light affording a key way of identifying material structures. In theories where both matter and light are treated quantum mechanically, the fundamental scattering process is represented as the concurrent annihilation of a photon from one radiation mode and creation of another in a different mode. Developing this quantum electrodynamical formulation, the focus of the present work is on the spectroscopic consequences of electrodynamic coupling between neighboring molecules or other kinds of optical center. To encompass these nanoscale interactions, through which the molecular states evolve under the dual influence of the input light and local fields, this work identifies and determines two major mechanisms for each of which different selection rules apply. The constituent optical centers are considered to be chemically different and held in a fixed orientation with respect to each other, either as two components of a larger molecule or a molecular assembly that can undergo free rotation in a fluid medium or as parts of a larger, solid material. The two centers are considered to be separated beyond wavefunction overlap but close enough together to fall within an optical near-field limit, which leads to high inverse power dependences on their local separation. In this investigation, individual centers undergo a Stokes transition, whilst each neighbor of a different species remains in its original electronic and vibrational state. Analogous principles are applicable for the anti-Stokes case. The analysis concludes by considering the experimental consequences of applying this spectroscopic interpretation to fluid media; explicitly, the selection rules and the impact of pressure on the radiant intensity of this process.
authors.affiliation: School of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom.
authors.forename: Mathew D
authors.initials: MD
authors.lastname: Williams
authors.affiliation: School of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom.
authors.forename: David S
authors.initials: DS
authors.lastname: Bradshaw
authors.affiliation: School of Chemistry, University of East Anglia, Norwich NR4 7TJ, United Kingdom.
authors.forename: David L
authors.initials: DL
authors.lastname: Andrews