Vibrational Modes and the Dynamic Solvent Effect in Electron and Proton Transfer

Barbara, Paul F.; Walker, Gilbert C.; Smith, Terrance P.

doi:10.1126/science.256.5059.975

Cited by 277 publications

(222 citation statements)

References 55 publications

(3 reference statements)

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“…[57][58][59] The Barbara and Yoshihara groups have made use of two-dimensional reaction-coordinate models in analyzing their ultrafast photoinduced electron-transfer rates for intra-and intermolecular reactions, respectively. 38,[43][44][45][46][47]50,52,[60][61][62][63][64][65][66][67] They have combined the models of Sumi and Marcus, 68 and of Bixon and Jortner,69,70 so that the electron-transfer reaction proceeds along or between two reaction coordinates: a solvation coordinate, and a vibrational coordinate. An important point is to decide whether the inertial components of solvation dynamics are included along the solvation coordinate or along the vibrational coordinate.…”

Section: Introductionmentioning

confidence: 99%

Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

2000

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We combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken-Hush (GMH) theory in the study of electron-transfer reactions and electron donoracceptor interactions. Our focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories: six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)-coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular dynamics trajectories, semiempirical quantum mechanical calculations (of the relevant adiabatic electronic states), and GMH theory to the C152/DMA photoreaction, we calculate the electron donor/acceptor interaction parameter H DA at various time frames. H DA is strongly modulated by both inner-sphere and outer-sphere nuclear dynamics, leading us to conclude that H DA must be considered as a dynamical variable.

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Section: Introductionmentioning

confidence: 99%

Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

2000

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“…Much of our understanding of chemical reaction dynamics has been acquired with ultrafast optical spectroscopy [65][66][67][68][69][70][71]. Of particular significance in these time-resolved studies has been the investigation of photodissociation and recombination [66,[70][71][72][73][74][75][76][77][78][79][80], photoisomerization [69,[81][82][83][84][85][86][87][88][89][90][91][92] and photoinitiated electron transfer reactions [67,68,[93][94][95][96] at surfaces and in liquids, glasses, solids and proteins. While these extensive investigations have led to a wealth of information regarding chemical reaction dynamics in the condensed phase, critical aspects of the dynamics and the influence of the environment on chemical and biological reactions have yet to be fully characterized experimentally.…”

Section: Structural Dynamics In Chemistry and Molecular Biologymentioning

confidence: 99%

X-ray free-electron lasers

Feldhaus

Arthur

Hastings

2005

J. Phys. B: At. Mol. Opt. Phys.

157

127

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In a free-electron laser (FEL) the lasing medium is a high-energy beam of electrons flying with relativistic speed through a periodic magnetic field. The interaction between the synchrotron radiation that is produced and the electrons in the beam induces a periodic bunching of the electrons, greatly increasing the intensity of radiation produced at a particular wavelength. Depending only on a phase match between the electron energy and the magnetic period, the wavelength of the FEL radiation can be continuously tuned within a wide spectral range. The FEL concept can be adapted to produce radiation wavelengths from millimetres toÅngstroms, and can in principle produce hard x-ray beams with unprecedented peak brightness, exceeding that of the brightest synchrotron source by ten orders of magnitude or more. This paper focuses on short-wavelength FELs. It reviews the physics and characteristic properties of single-pass FELs, as well as current technical developments aiming for fully coherent x-ray radiation pulses with pulse durations in the 100 fs to 100 as range. First experimental results at wavelengths around 100 nm and examples of scientific applications planned on the new, emerging x-ray FEL facilities are presented.

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“…This difficulty can be overcome by ultrafast nonlinear spectroscopies involving many laser interactions such as pump-probe spectroscopy. [13][14][15] These techniques make it possible to utilize more than one time-evolution period and allow us to distinguish dynamical processes with different time responses. Recently, two-dimensional (2D) electronic spectroscopy has also taken part in the investigation of the dynamics of exciton transfer [16][17][18][19] and electron transfer processes, 20,21 which stimulated the investigation of this field especially focusing on a role of quantum coherence.…”

Section: Introductionmentioning

confidence: 99%

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two-dimensional correlation spectroscopy

Tanimura

2012

The Journal of Chemical Physics

129

137

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Quantum heat current under non-perturbative and non-Markovian conditions: Applications to heat machinesWe theoretically investigate an electron transfer (ET) process in a dissipative environment by means of two-dimensional (2D) correlation spectroscopy. We extend the reduced hierarchy equations of motion approach to include both overdamped Drude and underdamped Brownian modes. While the overdamped mode describes the inhomogeneity of a system in the slow modulation limit, the underdamped mode expresses the primary vibrational mode coupled with the electronic states. We outline a procedure for calculating 2D correlation spectrum that incorporates the ET processes. The present approach has the capability of dealing with system-bath coherence under an external perturbation, which is important to calculate nonlinear response functions for non-Markovian noise. The calculated 2D spectrum exhibits the effects of the ET processes through the presence of ET transition peaks along the 1 axis, as well as the decay of echo signals.

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Vibrational Modes and the Dynamic Solvent Effect in Electron and Proton Transfer

Cited by 277 publications

References 55 publications

Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

Solvent as Electron Donor: Donor/Acceptor Electronic Coupling Is a Dynamical Variable

X-ray free-electron lasers

Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two-dimensional correlation spectroscopy

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