ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The quantum theory of light absorption by a pair of neighboring absorbers is developed in the point dipole approximation for the circumstance where excited states decay only by radiative damping. Comparison with classical local field theories, in which the monomers are represented by constant, frequency-dependent complex polarizabilities, shows that these local field theories are valid for non-harmonic absorbers only in the weak interaction limit, and only when there exist no states with both monomers simultaneously excited (e.g. one excited vibrationally, the other electronically) that are nearly degenerate with the single excitation states and also connected to them by appreciable transition moments. Failure of the local field theories is, thus, shown to be a consequence of the non-harmonic nature of real absorbers.Using a general relation between the level-shift function and complex polarizability, a recipe is formulated for calculating the complex polarizability and spectrum of a dimer.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560050104
Permalink
