Charge-transfer states and optical spectra in the condensed phase

1978 ◽  
Vol 28 (6) ◽  
pp. 718-721 ◽  
Author(s):  
N. A. Kirichenko ◽  
L. M. Blinov
Keyword(s):  
Charge Transfer ◽  
Condensed Phase ◽  
Optical Spectra

scholarly journals Combining Theory and Experiment for Understanding of Ultrafast Photoinduced Charge-Transfer Processes

2020 ◽  
pp. 91-99
Author(s):  
Eric Vauthey
Keyword(s):  
Charge Transfer ◽  
Condensed Phase ◽  
Photoinduced Charge Transfer ◽  
Transfer Processes ◽  
Experimental Spectroscopy ◽  
Photoinduced Charge ◽  
Theory And Experiment

This article gives a brief overview of the longstanding collaboration between our experimental spectroscopy group in Geneva and the theoretical group lead by Prof. A.I. Ivanov in Volgograd. This fruitful collaboration resulted in a significant increase of our understanding of the dynamics of several ultrafast chargetransfer processes in the condensed phase.

Effect of proton acceptors on the condensed phase radiolysis of cyclohexane-d12 in cyclopentane

1968 ◽  
Vol 46 (22) ◽  
pp. 3531-3535
Author(s):  
J. A. Stone
Keyword(s):  
Charge Transfer ◽  
Proton Transfer ◽  
Condensed Phase ◽  
Previous Suggestion ◽  
Resonance Charge

C2H5OH decreases the HD and D2 yields from small concentrations of c-C6D12 in c-C5H10. The results are consistent with a previous suggestion that the enhanced yields in this system are due to exothermic charge transfer. Charge transfer to c-C6D12 is only ~ 10% as efficient as proton transfer to C2H5OH at 4.1 mole % c-C6D12 or C2H5OH. Experiments at 196 and 77 °K suggest that resonance charge transfer in the cyclopentane matrix may occur to some extent.

scholarly journals Condensed Phase Laser Induced Harpoon Reactions

1988 ◽  
Vol 9 (1-3) ◽  
pp. 1-26 ◽  
Author(s):  
Mario E. Fajardo ◽  
R. Withnall ◽  
J. Feld ◽  
F. Okada ◽  
W. Lawrence ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Condensed Phase ◽  
Rare Gas ◽  
Many Body ◽  
Phase Dynamics ◽  
Two Photon ◽  
Radiation Fields ◽  
Electron Transitions ◽  
Charge Transfer Reactions

Laser induced charge transfer reactions of halogens in rare gas solids and liquids provide a powerful means for the study of condensed phase dynamics. Many-body effects with respect to both electronic and nuclear coordinates, and cooperative interactions with radiation fields, are some of the studied phenomena that are highlighted in this article.The pertinence of these ionic reactions to chemistry in solids is demonstrated in photodissociation studies of molecular halogens in rare gas matrices. The coexistence of both delocalized and localized charge transfer states in solid xenon doped with atomic halogens is presented and dynamical consequences—charge separation, self-trapping and energy storage—are discussed. Static and dynamic solvent effects in liquid phase harpoon reactions are considered. The characterization of cooperative excitations— two-photon, two-electron transitions—in liquid solutions is presented.

scholarly journals Nonlinear Spectroscopy in the Condensed Phase: The Role of Duschinsky Rotations and Third Order Cumulant Contributions

2020 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Excited State ◽  
Condensed Phase ◽  
Nonlinear Optical ◽  
Order Term ◽  
Optical Spectra ◽  
Cumulant Expansion ◽  
Third Order ◽  
The Third ◽  
Mode Mixing

First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. Here, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with a specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and Methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.

scholarly journals Nonlinear Spectroscopy in the Condensed Phase: The Role of Duschinsky Rotations and Third Order Cumulant Contributions

2020 ◽  
Author(s):  
Tim Zuehlsdorff ◽  
Hanbo Hong ◽  
Liang Shi ◽  
Christine Isborn
Keyword(s):  
Excited State ◽  
Condensed Phase ◽  
Nonlinear Optical ◽  
Order Term ◽  
Optical Spectra ◽  
Cumulant Expansion ◽  
Third Order ◽  
The Third ◽  
Mode Mixing

First-principles modeling of nonlinear optical spectra in the condensed phase is highly challenging because both environment and vibronic interactions can play a large role in determining spectral shapes and excited state dynamics. Here, we compute two dimensional electronic spectroscopy (2DES) signals based on a cumulant expansion of the energy gap fluctuation operator, with a specific focus on analyzing mode mixing effects introduced by the Duschinsky rotation and the role of the third order term in the cumulant expansion for both model and realistic condensed phase systems. We show that for a harmonic model system, the third order cumulant correction captures effects introduced by a mismatch in curvatures of ground and excited state potential energy surfaces, as well as effects of mode mixing. We also demonstrate that 2DES signals can be accurately reconstructed from purely classical correlation functions using quantum correction factors. We then compute nonlinear optical spectra for the Nile red and Methylene blue chromophores in solution, assessing the third order cumulant contribution for realistic systems. We show that the third order cumulant correction is strongly dependent on the treatment of the solvent environment, revealing the interplay between environmental polarization and the electronic-vibrational coupling.

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