Photoinduced electron transfer in isolated, jet-cooled molecular systems

Brenner, V.; Millié, P.; Piuzzi, F.; Tramer, A.

doi:10.1039/a701563a

Cited by 19 publications

(21 citation statements)

References 37 publications

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“…The changes of the internal structure of the complex' components would control the main parameters of the charge (electron) transfer reaction, i.e., the ionization potential of donor and electron affmity of acceptor molecules. Therefore, they would influence the energetics and rate constants of the reaction and if taken into account may be of use in the understanding of the initial step of photoinduced charge-transfer reaction, i.e., in the understanding of the changes of electronic and geometrical structure of EDA system in a transient state (an encounter complex) of the reaction [10,[13][14][15][16][17][18], as well as the experimentally observed [6,17,19] departures from the so-called two-state kinetic model of exciplex formation [20].…”

Section: Discussionmentioning

confidence: 99%

“…The electronic and geometrical structures of this transient state are not well-specified and are the key problems in the discussion of kinetics and dynamics of the photoinduced intermolecular electron (charge) transfer processes [10,[13][14][15][16][17][18]. However, in the discussion of the energetics of reaction (5) the important factors are its initial and final states.…”

Section: Exciplex Reaction and Me Changes Of Internal Structure Of Comentioning

confidence: 99%

“…Cases 2 and 3 are reflecting two possible initial states of reaction (5) as inferred and established by the spectroscopic investigations of jet-cooled exciplexes [10,[15][16][17]. In the case 2 the exciplex formation process is considered to begin from the non-relaxed excited Franck-Condon state of A*, i.e., the electron transfer process is a rapid one and it is followed by reorganization of the ion pair.…”

Section: Exciplex Reaction and Me Changes Of Internal Structure Of Comentioning

confidence: 99%

“…The experimental investigations of the excitation and fluorescence spectra of EDA systems indicate that vibrational frequencies of the component molecules are changing upon the formation of the complex [3,6,8]. This means that the internal structure of complex' components changes, however an estimation of the contribution of energy due to such changes to the energy of formation of CT state has been discussed only occasionally [9][10][11] and still remains an open question. This problem is the central issue of the present study and is quantitatively treated for the EDA system of 1,2,4,5-tetracyanobenzene (TCNB) and diethylaniline (DEA).…”

Section: Introductionmentioning

confidence: 99%

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Excited States of Intermolecular Electron-Donor-Acceptor Systems and Internal Geometry of Complex' Components

Deperasińska

Sobieraj

1999

Acta Phys. Pol. A

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In this work we present the results of semiempirical AM1 calculations of the energy of electron-donor-acceptor system in the ground and excited states with full optimization of the complex geometry (in terms of both: intermolecular and intramolecular coordinates). A comparison of these results with those obtained for separated acceptor and donor molecules enables the estimation of the energetic effects of changes in internal structure of donor and acceptor which accompany the process of formation and stabilization of excited charge-transfer state. It is shown that energies corresponding to those changes are comparable with the energy of intermolecular interactions between donor and acceptor molecules.

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Section: Discussionmentioning

confidence: 99%

Section: Exciplex Reaction and Me Changes Of Internal Structure Of Comentioning

confidence: 99%

Section: Exciplex Reaction and Me Changes Of Internal Structure Of Comentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Excited States of Intermolecular Electron-Donor-Acceptor Systems and Internal Geometry of Complex' Components

Deperasińska

Sobieraj

1999

Acta Phys. Pol. A

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“…In the gas phase, for the effective formation of exciplexes higher elasticities of vapors than those used by us are needed. In vapors, it is possible to observe fluorescence of only relatively strong excited complexes because of their fast dissociation at high temperatures [21,22]. The conditions for the formation of stable complexes in the gas phase are improved only in the cases of strong cooling of molecules in supersonic jets [22].…”

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confidence: 99%

Intermolecular Processes in Excited Electronic States in the Gas Phase (Review)

Zalesskaya

Sambor

2005

J Appl Spectrosc

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A brief review of works on the temperature dependences of the rate constants k q of the intermolecular processes proceeding in the excited electronic states in the gas phase is given. The dependences k q (T) for such biomolecular processes as intermolecular vibrational energy transfer in the triplet state vibrational quasi-continuum, triplet-triplet electron excitation energy transfer, and intermolecular photoinduced electron transfer have been compared. The experimental data have shown that in the gas phase for all analyzed intermolecular processes both an increase and a decrease in k q with increasing temperature (T) is observed, which is not associated with the specific intermolecular interactions leading to the formation of long-lived components. The change in the type of temperature dependence is due to the change in the mechanisms of the radiationless transitions with increasing density of vibrational levels in the final electronic state. The applicability of the known models based on the theory of radiationless transitions for predicting the temperature dependences k q (T) is discussed.Keywords: temperature dependence of the rate constants of intermolecular processes, intermolecular vibrational energy transfer, triplet-triplet energy transfer, photoinduced intermolecular electron transfer.Introduction. Biomolecular processes play an important part in gaseous media such as the atmosphere, gaseous mixtures resulting from combustion and explosions, working mixtures of gas lasers, gaseous mixtures of isotopes, etc. In real molecular mixtures, the yield of photochemical reactions depends on the efficiency of the electron and vibrational energy exchange and transfer. The temperature dependences of the probability of collisional processes are of fundamental interest both for studying the nature of intermolecular interactions deactivating excited molecules and testing theoretical models. The practical interest in such studies is primarily due to the necessity of estimating the yield of gas-phase reactions in a wide range of temperatures.In analyzing the intermolecular processes in the excited electronic states, it is usually assumed that their rates increase with increasing temperature. Negative temperature dependences are considered as a result of specific intermolecular interactions leading to the formation of stable complexes of various nature. The most detailed theoretical studies of the temperature dependence of the energy transfer probability have been made for the intermolecular vibrational relaxation of small molecules in the system of discrete vibrational levels [1]. It has been shown that for this intermolecular process both positive and negative temperature dependences of the rate constants and the energy transfer efficiencies are possible. For the triplet-triplet (T-T) electron excitation energy transfer and the intermolecular photoinduced electron transfer (PET), the possibilities of modeling the temperature changes in the process probability were discussed only for some special cases in [2] and [3, 4...

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