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Title: Intermolecular interactions in a radiation field via the method of induced moments

Abstract

Molecular quantum electrodynamics is employed to calculate a generalized formula for the energy shift between a pair of molecules that have electric polarizability of arbitrary multipole order and are in the presence of an intense electromagnetic field. In contrast to a previous calculation of the dipole-dipole contribution, which required fourth-order time-dependent perturbation theory for its evaluation, the present approach involves calculating the interaction between the multipole moments induced at each center by the incident beam and the resonant multipole-multipole coupling tensor together with the average value of the spatial correlation function of the displacement field for an N-photon state. The theory developed applies to the situation where the molecular pair is held fixed relative to the direction of propagation of the radiation field or is allowed to be completely randomly oriented. Explicit results are obtained for dipole-quadrupole and quadrupole-quadrupole polarizable molecules. For oriented systems the energy shift for linear and circular polarizations is examined for incident radiation propagating in directions parallel and perpendicular to the intermolecular join, and the asymptotic behavior is obtained at the limits of short and large separation distance. After performing a pair orientation average, the energy shift in the near zone is found to exhibit anmore » R{sup -1} power-law behavior with separation distance, while the far zone has a modulated R{sup -2} dependence in all of the cases considered. None of the energy shifts obtained display discriminatory characteristics, with respect to either the handedness of the incident beam or the individual species.« less

Authors:
 [1]
  1. Department of Chemistry, Wake Forest University, Winston-Salem, North Carolina 27109-7486 (United States)
Publication Date:
OSTI Identifier:
20786735
Resource Type:
Journal Article
Journal Name:
Physical Review. A
Additional Journal Information:
Journal Volume: 73; Journal Issue: 1; Other Information: DOI: 10.1103/PhysRevA.73.013406; (c) 2006 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 1050-2947
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; CORRELATION FUNCTIONS; COUPLING; DIPOLES; ELECTROMAGNETIC FIELDS; EVALUATION; MOLECULES; ORIENTATION; PERTURBATION THEORY; PHOTONS; POLARIZABILITY; POLARIZATION; QUADRUPOLES; QUANTUM ELECTRODYNAMICS; TENSORS; TIME DEPENDENCE

Citation Formats

Salam, A. Intermolecular interactions in a radiation field via the method of induced moments. United States: N. p., 2006. Web. doi:10.1103/PHYSREVA.73.0.
Salam, A. Intermolecular interactions in a radiation field via the method of induced moments. United States. https://doi.org/10.1103/PHYSREVA.73.0
Salam, A. Sun . "Intermolecular interactions in a radiation field via the method of induced moments". United States. https://doi.org/10.1103/PHYSREVA.73.0.
@article{osti_20786735,
title = {Intermolecular interactions in a radiation field via the method of induced moments},
author = {Salam, A},
abstractNote = {Molecular quantum electrodynamics is employed to calculate a generalized formula for the energy shift between a pair of molecules that have electric polarizability of arbitrary multipole order and are in the presence of an intense electromagnetic field. In contrast to a previous calculation of the dipole-dipole contribution, which required fourth-order time-dependent perturbation theory for its evaluation, the present approach involves calculating the interaction between the multipole moments induced at each center by the incident beam and the resonant multipole-multipole coupling tensor together with the average value of the spatial correlation function of the displacement field for an N-photon state. The theory developed applies to the situation where the molecular pair is held fixed relative to the direction of propagation of the radiation field or is allowed to be completely randomly oriented. Explicit results are obtained for dipole-quadrupole and quadrupole-quadrupole polarizable molecules. For oriented systems the energy shift for linear and circular polarizations is examined for incident radiation propagating in directions parallel and perpendicular to the intermolecular join, and the asymptotic behavior is obtained at the limits of short and large separation distance. After performing a pair orientation average, the energy shift in the near zone is found to exhibit an R{sup -1} power-law behavior with separation distance, while the far zone has a modulated R{sup -2} dependence in all of the cases considered. None of the energy shifts obtained display discriminatory characteristics, with respect to either the handedness of the incident beam or the individual species.},
doi = {10.1103/PHYSREVA.73.0},
url = {https://www.osti.gov/biblio/20786735}, journal = {Physical Review. A},
issn = {1050-2947},
number = 1,
volume = 73,
place = {United States},
year = {2006},
month = {1}
}