The transition from non-adiabatic to solvent controlled adiabatic electron transfer kinetics. An experimental study

Masad, Asnat; Huppert, Dan; Kosower, Edward M.

doi:10.1016/0301-0104(90)80105-7

Cited by 22 publications

(11 citation statements)

References 51 publications

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“…219 A transition from a nonadiabatic to a solventcontrolled adiabatic regime was also shown to be feasible upon lowering temperature, and slowing down dielectric relaxation. 220 Additionally, the fluorescence decay of the LE state of N-aryl-aminonaphthalenesulfonates in pentanediol was found to be nonexponential and to be reproducible using a stretched exponential function with a time constant equal to τ l . 221 This nonexponential character was ascribed to a distribution of effective solvation times due to specific H-bond solute−solvent interactions.…”

Section: Intramolecular Electron Transfermentioning

confidence: 97%

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

et al. 2016

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Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha-Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis-trans isomerizations, respectively.

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Section: Intramolecular Electron Transfermentioning

confidence: 97%

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

et al. 2016

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“…the time constants of ultrafast ET processes are found to correlate with the relaxation time of the solvent in which the reaction takes place (72)(73)(74). This is, for example, the case with 3-( p-N,N-dimethylaminophenyl)perylene (PeDMA) (Figure 3) for which intramolecular CS from the dimethylaniline to the excited perylene units takes place with time constants of approximately 700 fs, 2.2 ps, and 72 ps in acetonitrile, DMSO (dimethylsulfoxide), and 1-butanol, respectively, whereas the average solvation times, τ s , amount to 260 fs, 2 ps, and 103 ps (75).…”

Section: Electron Transfermentioning

confidence: 98%

Ultrafast Photochemistry in Liquids

Rosspeintner

Lang

Vauthey

2013

Annu. Rev. Phys. Chem.

165

160

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Ultrafast photochemical processes can occur in parallel with the relaxation of the optically populated excited state toward equilibrium. The latter involves both intra- and intermolecular modes, namely vibrational and solvent coordinates, and takes place on timescales ranging from a few tens of femtoseconds to up to hundreds of picoseconds, depending on the system. As a consequence, the reaction dynamics can substantially differ from those usually measured with slower photoinduced processes occurring from equilibrated excited states. For example, the decay of the excited-state population may become strongly nonexponential and depend on the excitation wavelength, contrary to the Kasha and Vavilov rules. In this article, we first give a brief account of our current understanding of vibrational and solvent relaxation processes. We then present an overview of important classes of ultrafast photochemical reactions, namely electron and proton transfer as well as isomerization, and illustrate with several examples how nonequilibrium effects can affect their dynamics.

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“…When the ET rate constant is comparable to or faster than that for solvent dynamics, the solvent controlled adiabatic mechanism prevails; only in this case does the timescale at which the reactant system approaches the transition state become rate-determined by solvent friction. The transition from a nonadiabatic to a solvent controlled adiabatic ET reaction mechanism is thus possible when the timescale of the ET reaction has relatively weak temperature dependence, and coincides with that of solvent dynamics [283][284][285][286][287].…”

Section: Coupling Charge Transfer and Solvation Dynamics; The Solventmentioning

confidence: 98%

Electron transfer reactions of rigid, cofacially compressed, π-stacked porphyrin–bridge–quinone systems

Kang

Iovine

Therien

2011

Coordination Chemistry Reviews

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The transition from non-adiabatic to solvent controlled adiabatic electron transfer kinetics. An experimental study

Cited by 22 publications

References 51 publications

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

Ultrafast Photochemistry in Liquids

Electron transfer reactions of rigid, cofacially compressed, π-stacked porphyrin–bridge–quinone systems

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