Resonance Raman Intensities and Charge-Transfer Reorganization Energies

Myers, Anne B.

doi:10.1021/cr950249c

Cited by 283 publications

(302 citation statements)

References 123 publications

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“…This approximation has been used successfully for describing Franck-Condon and resonance Raman spectra. 89 It is also employed in the linear vibronic coupling model of conical intersections 90 and in the Marcus theory of ET. Within the description of the nuclear degrees of freedom employed here, the parameters of the diabatic potential energy surfaces of the donor and acceptor states are obtained from the potential energy functions of the excited state of the neutral dye molecule and the ground state of its cation, respectively.…”

Section: Characterization Of Nuclear Degrees Of Freedommentioning

confidence: 99%

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

Wang

Persson

et al. 2012

The Journal of Chemical Physics

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Photoinduced electron transfer processes in perylene-titanium dioxide dye-semiconductor systems are studied. In particular, the influence of saturated and unsaturated aliphatic spacer groups inserted between the chromophore and the semiconductor substrate is investigated. The study is based on a recently developed method that combines first-principles electronic structure calculations to characterize the dye-semiconductor systems and accurate multilayer multiconfiguration time-dependent Hartree simulations to reveal the underlying nonadiabatic dynamics. The results show that, in agreement with previous experimental studies, the spacer groups may affect the electron transfer dynamics significantly. Furthermore, the influence of electronic-vibrational coupling on the electron transfer dynamics and absorption spectra is discussed.

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Section: Characterization Of Nuclear Degrees Of Freedommentioning

confidence: 99%

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

Wang

Persson

et al. 2012

The Journal of Chemical Physics

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“…Ideally, a starting nuclear distortion with high intensity is available as a starting guess. For Resonance Raman spectroscopy, a high-intensity starting guess has been derived [30] in the framework of Heller's shorttime approximation [68,69] and successfully applied in IntensityTracking iterations. [30] In this case, the direction of the gradient of the electronically excited state leading to the resonance enhancement is taken as the starting nuclear distortion.…”

Section: Intensity-trackingmentioning

confidence: 99%

MOVIPAC: Vibrational spectroscopy with a robust meta‐program for massively parallel standard and inverse calculations

et al. 2012

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We present the software package MOVIPAC for calculations of vibrational spectra, namely infrared, Raman, and Raman Optical Activity (ROA) spectra, in a massively parallelized fashion. MOVIPAC unites the latest versions of the programs SNF and AKIRA alongside with a range of helpful add-ons to analyze and interpret the data obtained in the calculations. With its efficient parallelization and meta-program design, MOVIPAC focuses in particular on the calculation of vibrational spectra of very large molecules containing on the order of a hundred atoms. For this purpose, it also offers different subsystem approaches such as Mode-and Intensity-Tracking to selectively calculate specific features of the full spectrum. Furthermore, an approximation to the entire spectrum can be obtained using the Cartesian Tensor Transfer Method. We illustrate these capabilities using the example of a large p-helix consisting of 20 (S)-alanine residues. In particular, we investigate the ROA spectrum of this structure and compare it to the spectra of aand 3 10 -helical analogs.

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“…In the time-dependent theory of resonance Raman scattering, the energy denominator of the resonant term can be expressed as a half-Fourier transform. Equation (1) can then be rewritten in its most compact form as Equation (2): [8,[39][40][41] …”

Section: Theoretical Background Of Rr Calculationsmentioning

confidence: 99%

The Resonance Raman Spectra of Spheroidene Revisited with a First‐Principles Approach

2011

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The resonance Raman (RR) spectra of different configurations of spheroidene are calculated by means of quantum chemical methods to investigate the nature of the cis configuration of this carotenoid molecule in the photosynthetic reaction center (RC) of the purple bacterium Rhodobacter sphaeroides. For validation of our methodology, we also calculate the spectrum of the all-trans structure present in the light-harvesting complexes of this bacterium. While former theoretical resonance Raman studies only considered truncated models of spheroidene, we report on calculations employing the full pigment here. The calculated frequencies for the all-trans configuration are in good agreement with former experimental and simulated data. Among the possible cis structures, the 15,15'-cis configuration shows a RR spectrum that is in best agreement with the experimental spectrum of spheroidene in the RC. In order to assess model truncation effects, we compare calculations for the full spheroidene molecule to those for the truncated model. While the main features can already be found in the latter, the full model leads to considerably different intensities in the region around 1150 cm(-1), which improve the agreement with experiment. A slight mismatch for the vibrational frequencies in the C=C stretch region is investigated by considering a model for spheroidene in the binding pocket comprising more than 500 atoms in total. The results do not lead to improved agreement with experiment, in contrast to the simpler strategy of introducing constraints in the structural optimization of a truncated spheroidene model. The calculated RR spectrum of the 13,14-cis configuration shows additional features which can also be identified in the experimental RR spectrum. This shows that the most likely cis structure is the 15,15'-cis configuration. Besides this, the 13,14-cis configuration remains a candidate for an additional spheroidene structure in the RC of Rhodobacter sphaeroides mutant R26.

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Resonance Raman Intensities and Charge-Transfer Reorganization Energies

Cited by 283 publications

References 123 publications

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

Photoinduced electron transfer processes in dye-semiconductor systems with different spacer groups

MOVIPAC: Vibrational spectroscopy with a robust meta‐program for massively parallel standard and inverse calculations

The Resonance Raman Spectra of Spheroidene Revisited with a First‐Principles Approach

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