@article{gao_aspnes_franzen_2022, title={Classical Model of Surface Enhanced Infrared Absorption (SEIRA) Spectroscopy}, volume={1}, ISSN={["1520-5215"]}, DOI={10.1021/acs.jpca.1c08463}, abstractNote={The molecule-plasmon interaction is the key to the mechanisms of surface enhanced infrared absorption (SEIRA) and surface enhanced Raman scattering (SERS). Since plasmons are well described by Maxwell's equations, one fundamental treatment involves the classical interpretation of infrared absorption and resonance Raman spectroscopies. We can understand the molecule-plasmon interaction using electromagnetic theory if the classical field effect on a transition dipole moment or transition polarizability is properly described. In previous work, we derived the Raman excitation profile of a model molecule using a classical driven spring attached to a charged mass with a perturbative force constant due to vibrational oscillations. In this study we generalize the interactions of plasmons with molecules by considering the N2O asymmetric stretch SEIRA signal on a Dy doped CdO (CdO:Dy) film. This semiconductor has tunable plasmon dispersion curves throughout the near-and mid-infrared that can interact directly with vibrational absorption transitions. We have demonstrated this using the Kretschmann configuration with a CaF2 prism and a MgO substrate. The model predicts the phase behavior of SEIRA. The calculated enhancement factor relative to an Au control is 6.2, in good agreement with the value of 6.8 ± 0.5 measured under the same conditions.}, journal={JOURNAL OF PHYSICAL CHEMISTRY A}, author={Gao, Yuan and Aspnes, D. E. and Franzen, Stefan}, year={2022}, month={Jan} }
@article{gao_aspnes_franzen_2020, title={Classical Correlation Model of Resonance Raman Spectroscopy}, volume={124}, ISSN={["1520-5215"]}, DOI={10.1021/acs.jpca.0c04401}, abstractNote={A classical correlation model (CCM), based on forces instead of potentials, is developed and applied to resonance Raman scattering to provide a foundation for further advances in understanding the effects of fields and vibronic perturbations on the optical properties of materials by a simple, yet versatile, description. The model consists of a charge connected by a classical spring to a surface and driven by an external electric field. The spring represents the charge cloud of the electrons and the transition strength, and the surface represents the nucleus or molecule. Molecular vibrations are assumed to be many-body effects that change the configuration and hence modify the spring constant directly, as opposed to all previous classical models of Raman scattering, and opposed to the anisotropic bond model (ABM) of nonlinear optics, by adding anharmonic terms to the potential. The resulting expression agrees exactly with quantum mechanical models of resonance Raman scattering in the limit of weak electron-phonon coupling, and it agrees well when the coupling becomes strong. The result is a classical derivation of Kramers-Heisenberg-Dirac scattering theory. We show that the difference between classical and quantum approaches lies only in the interpretation of the prefactor. In particular, the Raman excitation profile shows excellent agreement with all other methods of calculation. By comparing complementary classical and quantum solutions of the same complex system, understanding of both is enhanced.}, number={44}, journal={JOURNAL OF PHYSICAL CHEMISTRY A}, author={Gao, Y. and Aspnes, D. E. and Franzen, S.}, year={2020}, month={Nov}, pages={9177–9186} }