Resonance Raman Intensity Analysis of Vibrational and Solvent Reorganization in Photoinduced Charge Transfer

Abstract

Quantitative analysis of resonance Raman scattering cross sections, together with charge-transfer absorption and emission spectra, can provide detailed information about the changes in nuclear equilibrium geometry undergone by both the electron donor and acceptor and the surrounding solvent in photoinduced charge-transfer processes. The molecular parameters that determine absorption and fluorescence band shapes and resonance Raman cross sections are summarized, and methods for extracting those parameters through spectral modeling are reviewed with emphasis on charge-transfer systems. Applications to the determination of molecular and solvent reorganization parameters to several organic intra- and intermolecular charge-transfer transitions are then presented, and prospects for further development of the technique are discussed.

Communication: Uncovering molecule-TiO2 interactions with nonlinear spectroscopy

“…As in a resonance Raman experiment, the vibrational amplitude reflects the magnitude of the displacement in potential energy surfaces corresponding to the ground and excited electronic states. 27 What makes our findings particularly interesting is that the nuclear mode is localized in TiO 2 . Displacement in this mode makes clear that the electronic excitation produces a fairly significant change in the charge distribution within TiO 2 .…”

Initial Excited-State Structural Dynamics of 6-Substituted Uracil Derivatives: Femtosecond Angle and Bond Lengthening Dynamics in Pyrimidine Nucleobase Photochemistry

“…The general implementation of these equations for absorption and resonance Raman spectroscopy have been described in detail previously. [4][5][6][7][8][9][10][11][12][13][14]16,17 The vibrational mode assignments described in Tables 1 and 2 were obtained by DFT computation at the B3LYP/6-311G(d,p) level of theory, with the default gradients implemented in the Gaussian09 18 package performed on the initial planar C s structures of uracil and 6-MeU in the diketo tautomer form. The isotope effect was calculated for 6-d-U from the uracil frequencies, which are not scaled.…”

Pure and mixed films of a nitrostilbene derivative at the air–water interface, Langmuir–Blodgett multilayer fabrication, and optical characterization

“…Thus, a typical push-pull stilbene, 4-amino-4 -nitrostilbene, has been recently calculated to have [23] a molecular quadratic hyperpolarizability, β, as high as 200 × 10 −30 esu. Push-pull chromophores also serve as solvation probes [24,25] and as model systems for electron transfer [26][27][28].…”