Solvation dynamics for an ion pair in a polar solvent: Time‐dependent fluorescence and photochemical charge transfer

1991 ◽  
Vol 94 (9) ◽  
pp. 5961-5979 ◽  
Author(s):  
Emily A. Carter ◽  
James T. Hynes
Keyword(s):  
Charge Transfer ◽  
Polar Solvent ◽  
Ion Pair ◽  
Time Dependent ◽  
Solvation Dynamics

Photoinduced Charge Transfer Dynamics in Carotenoid-Porphyrin-C60 Triad via the Linearized Semiclassical Nonequilibrium Fermi's Golden Rule

2020 ◽  
Author(s):  
Zhengqing Tong ◽  
Margaret S. Cheung ◽  
Barry D. Dunietz ◽  
Eitan Geva ◽  
Xiang Sun
Keyword(s):  
Charge Transfer ◽  
Golden Rule ◽  
Time Dependent ◽  
Rate Coefficients ◽  
Initial State ◽  
Photoinduced Charge Transfer ◽  
Transfer Rates ◽  
Fermi's Golden Rule ◽  
Photoinduced Charge ◽  
Fermi’S Golden Rule

The nonequilibrium Fermi’s golden rule (NE-FGR) describes the time-dependent rate coefficient for electronic transitions, when the nuclear degrees of freedom start out in a <i>nonequilibrium</i> state. In this letter, the linearized semiclassical (LSC) approximation of the NE-FGR is used to calculate the photoinduced charge transfer rates in the carotenoid-porphyrin-C<sub>60</sub> molecular triad dissolved in explicit tetrahydrofuran. The initial nonequilibrium state corresponds to impulsive photoexcitation from the equilibrated ground-state to the ππ* state, and the porphyrin-to-C<sub>60</sub> and the carotenoid-to-C<sub>60</sub> charge transfer rates are calculated. Our results show that accounting for the nonequilibrium nature of the initial state significantly enhances the transition rate of the porphyrin-to-C<sub>60</sub> CT process. We also derive the instantaneous Marcus theory (IMT) from LSC NE-FGR, which casts the CT rate coefficients in terms of a Marcus-like expression, with explicitly time-dependent reorganization energy and reaction free energy. IMT is found to reproduce the CT rates in the system under consideration remarkably well.

Impact of vibronic coupling effects on light-driven charge transfer in pyrene-functionalized middle and large-sized Metalloid Gold Nanoclusters from Ehrenfest dynamics.

2021 ◽  
Author(s):  
Adrian Dominguez-Castro ◽  
Thomas Frauenheim
Keyword(s):  
Molecular Dynamics ◽  
Charge Transfer ◽  
Density Functional ◽  
Theoretical Calculations ◽  
Gold Nanoclusters ◽  
Tight Binding ◽  
Time Dependent ◽  
Effective Strategy ◽  
Dynamics Simulations ◽  
Dependent Density

Theoretical calculations are an effective strategy to comple- ment and understand experimental results in atomistic detail. Ehrenfest molecular dynamics simulations based on the real-time time-dependent density functional tight-binding (RT-TDDFTB) approach...

Charge-transfer stabilization of molecular bicimers: ion pair formation in diarylmethanes

1988 ◽  
Vol 92 (7) ◽  
pp. 1703-1705 ◽  
Author(s):  
R. J. Locke ◽  
Steve H. Modiano ◽  
E. C. Lim
Keyword(s):  
Charge Transfer ◽  
Ion Pair ◽  
Pair Formation ◽  
Ion Pair Formation

Bisporphyrin connected by tetrathiafulvalene

2009 ◽  
Vol 13 (01) ◽  
pp. 114-121 ◽  
Author(s):  
Kazuya Ogawa ◽  
Yasunori Nagatsuka
Keyword(s):  
Cross Section ◽  
Density Functional ◽  
Polar Solvent ◽  
Soret Band ◽  
Oxidation Potential ◽  
Time Dependent ◽  
Photon Absorption ◽  
Functional Theory ◽  
Two Photon Absorption ◽  
Two Photon

A new porphyrintetrathiafulvalene composite, where two porphyrins are bridged by te trathiafulvalene (TTF) using acetylene bonds was synthesized. The Q-band of the monomeric porphyrin appears at 590 nm whereas that of the composite is red-shifted to 620 nm and intensified. The Soret band is also red-shifted from 427 nm to 435 nm and much broadened, indicating the expansion of π-conjugation over the porphyrin and tetrathiafulvalene units. The HOMOs and LUMOs were calculated using time-dependent density functional theory. Voltammetric experiments revealed that the first oxidation potential of the TTF moiety in the composite was shifted by +155 mV compa red with TTF in the absence of composite. The effective two-photon absorption (2PA) cross section values were measured by using a nanosecond open aperture Z-scan method. The maximum effective 2PA cross section values were obtained at 760 nm, as 7300 GM in benzonitrile and 5900 GM in toluene. The values obtained in the polar solvent were 1.2 to 1.5 times larger than those in the nonpolar solvent.

TIME DEPENDENT DENSITY FUNCTIONAL METHODS AND THEIR APPLICATION TO CHEMICAL PHYSICS

2004 ◽  
Vol 03 (01) ◽  
pp. 117-144 ◽  
Author(s):  
AKIRA YOSHIMORI
Keyword(s):  
Density Functional ◽  
Nonlinear Effects ◽  
Functional Method ◽  
Time Dependent ◽  
Solvation Dynamics ◽  
Chemical Physics ◽  
Functional Theory ◽  
Polar Liquids ◽  
Density Functional Methods ◽  
Functional Methods

This article reviews microscopic development of time dependent functional method and its application to chemical physics. It begins with the formulation of density functional theory. The time dependent extension is discussed after the equilibrium formulation. Its application is explained by solvation dynamics. In addition, it reviews studies of nonlinear effects on polar liquids and simple mixtures.

Sign in / Sign up

Export Citation Format

Share Document