Date of Award
1988
Degree Type
Dissertation
Degree Name
Doctor of Philosophy
Abstract
An analytic expression for the absorption spectra of a two-level molecule or atom is derived, within the rotating wave approximation (RWA), which includes the effects of permanent dipole moments and static electric fields. The derivation is for the interaction of the system with a plane-polarized sinusoidal electromagnetic field (EMF) in the semi-classical electric dipole approximation. The RWA resonance profile, and a series of exactly calculated two-level model spectra, are used to investigate some single- and multi-photon spectral effects due to permanent dipoles and static fields, relative to the atomic problem (no permanent dipoles). These effects include the occurrence of even as well as odd photon transitions. Permanent dipole moments can cause narrowing of the resonances, oscillatory fringes around the resonances as a function of frequency, and decreases in the molecule-EMF coupling, relative to the atomic results. Comparisons with exact two-level model spectra are used to study the validity of the RWA results and indicate that several features, such as dynamic backgrounds and shifts of the resonance frequencies from the weak EMF limits of {dollar}\omega\sbsp{lcub}\rm res{rcub}{lcub}\rm N{rcub}{dollar} = {dollar}\Delta{dollar}E/N, N = 1,2,3, dots, are missing in the RWA spectra as the coupling increases.;Perturbative corrections to the RWA absorption spectra and the full widths at half maxima for the resonances are derived, neglecting static fields, and used to investigate and explain the effects missing in the RWA; the RWA resonance profile is a zeroth plus first order result obtainable from a time-independent Floquet Hamiltonian secular equation. The usefulness and validity of the perturbative corrections are investigated and it is concluded that these corrections are not useful computationally past second order. However, the corrections are useful in understanding some of the deficiencies of the RWA. These include the shifts of the N-photon resonance positions to low frequency, with respect to {dollar}\Delta{dollar}E/N, that can occur for molecules with non-zero permanent dipoles; the shift is always to high frequency for atoms. A series of exact model calculations, for "giant dipole" molecules, is also used to discuss the effects of permanent dipole moments on spectra and to establish comparisons with the recent literature on the subject.
Recommended Citation
Kmetic, Mary Ann, "Effects Of Permanent Dipoles And Static Fields On Molecular Spectra" (1988). Digitized Theses. 1760.
https://ir.lib.uwo.ca/digitizedtheses/1760