Ultrafast electron dynamics at ice-metal interfaces: competition between heterogeneous electron transfer and solvation

Microscopic insight into heterogeneous electron transfer requires an understanding of the participating donor and acceptor states and of their respective interaction. In the regime of strong electronic coupling, two limits have been discussed where either the states overlap directly or the states are separated by a potential barrier. In both situations, the transfer probability is determined by the magnitude of the wave function overlap, whereby in the case of the potential barrier, its width and height are rate limiting. In our study, we observe a dynamical crossover between these two regimes by investigating the electron-transfer dynamics of localized, solvated electrons at ice-metal interfaces. Employing femtosecond time-resolved two-photon photoelectron spectroscopy, we analyze the population dynamics of excess electrons in the ice layer, which experience the competing processes of transfer to the metal electrode and energetic stabilization in the ice by molecular reorientation. Comparing the dynamics of D(2)O on Cu(111) and Ru(001), we observe an early regime at t < 300 fs, where the transfer time is determined by wave-function overlap with the metal and a second regime (t > 300 fs), where the transfer proceeds nearly independent of the substrate. The assignment of these two regimes to the established mechanisms of electron transfer is backed by an empirical model calculation that reproduces the experimental data in an excellent manner.     

A general theoretical model for electron transfer reactions in complex systems

In this paper we present a general theoretical-computational model for treating electron transfer reactions in complex atomic-molecular systems. The underlying idea of the approach, based on unbiased first-principles calculations at the atomistic level, utilizes the definition and the construction of the Diabatic Perturbed states of the involved reactive partners (i.e. the quantum centres in our perturbation approach) as provided by the interaction with their environment, including their mutual interaction. In this way we reconstruct the true Adiabatic states of the reactive partners characterizing the electron transfer process as the fluctuation of the electronic density due to the fluctuating perturbation. Results obtained by using a combination of Molecular Dynamics simulation and the Perturbed Matrix Method on a prototypical intramolecular electron transfer (from 2-(9,9'-dimethyl)fluorene to the 2-naphthalene group separated by a steroidal 5-α-androstane skeleton) well illustrate the accuracy of the method in reproducing both the thermodynamics and the kinetics of the process.     

Solvent effects on simple electron transfer reactions: A comparison of results for homogeneous and heterogeneous systems

Solvent effects on the rate constants for both homogeneous and heterogeneous electron transfer reactions have been analyzed on the basis of current models which consider the role of dynamic relaxation processes in determining the magnitude of the pre-exponential factor. A statistical method for separating the effects of the solvent longitudinal relaxation time τ_L from those of the solvent permittivity parameter γ is described and applied to 15 sets of experimental data for which results are available in at least four solvents. The degree to which the explained variation in the logarithm of the rate constant could be attributed to either of these effects varied all the way from 0 to 100% depending on the degree of reaction adiabaticity and the relative sizes of the inner and outer sphere components of the Gibbs energy of activation. Data for the limiting cases in which there is no τ_l dependence in the pre-exponential factor or in which the pre-exponential factor is proportional to τ_L⁻¹ were analyzed further to obtain the size-distance parameter and the components of the pre-exponential factor relevant to the encounter pre-equilibrium model. These parameters have been discussed with respect to current developments in electron transfer theory. Problems in estimating the longitudinal relaxation time in the solvent, required for the analysis, are also considered.     

Absorption spectra related to heterogeneous electron transfer reactions: the perylene TiO2 system

Linear absorption spectra of dye-semiconductor systems (perylene attached to nanostructured TiO2) are studied theoretically and experimentally. The systems show ultrafast photoinduced heterogeneous electron transfer (HET). By applying a time-dependent formulation of the absorbance, the theoretical analysis of the measured data is carried out. The respective electron-vibrational wave packet propagation fully accounts for the electronic coupling to the conduction band continuum of TiO2 and is based on a single-reaction-coordinate model (corresponding to a perylene in-plane C-C stretching vibration with a quantum energy of 1370 cm(-1)). By the insertion of different bridge-anchor groups, the electronic coupling responsible for HET is varied. The dye absorbance in a solvent and the trends in the line broadening of the vibrational progression due to the coupling to the conduction band continuum are reproduced for all investigated types of bridge-anchor groups. HET rates deduced from the calculations on the absorbance displaying line broadenings follow the qualitative trend obtained from transient absorption spectra.     

Theoretical studies of intramolecular electron transfer reactions: Distance and free energy dependences

Electron tunneling through a square potential energy barrier is used to calculate the distance-dependent factors of electron transfer (ET) processes in metal-monolayer-metal junctions, donors and acceptors dispersed in rigid organic glasses, intramolecular ET in rigid donorbridge—acceptor species in solution and redox centers attached to electrodes through adsorbed monolayers. This tunneling model of distancedependent non-adiabatic factors is incorporated in the intersecting state model (ISM). The result is a simple semiclassical theory which is used to calculate the rates of non-adiabatic ET reactions. When the electron is originally located in a π* molecular orbital of the donor and the reaction free energy is no lower than approximately −50 kJ mol⁻¹, no adjustable parameters are necessary to calculate the intramolecular ET rates from a donor, through a rigid bridge, to an acceptor. Such calculated rates are within an order of magnitude of the experimental values. The model can also account for the ET rates of more exothermic reactions provided that the value of an empirical parameter, which is constant for structurally related reactants and solvents of similar polarity, is estimated. The physical meaning of this parameter is related to the dynamics of the reactions. The profiles of the distance and free energy dependences of photoinduced ET rates are closely reproduced. The occurrence of distance-dependent non-adiabatic factors in intermolecular σ*-d ETs is rationalized.     

Polarographic studies of chemical reactions preceding electron transfer (review)

The review is dedicated to theory and experimental applications of polarography for studies of consecutive and parallel chemical reactions preceding electron transfer and occurring in the bulk or surface (adsorption) reaction layers. The methodology of finding kinetic and equilibrium parameters including formal potentials is presented. The following chemical reactions are considered: (1) protonation of anions of benzene polycarboxylic acids; (2) dehydration (decyclization) and protonation of carbonyl compounds; (3) proton exchange between mixed solvent molecules; (4) formaldehyde-amine interaction; (5) complexation with the ligand catalyzing electroreduction of metal ions; (6) dissociation of metal complexes; (7) formation of deposits of metal hydroxides with parallel oxygen reduction.     

Ultrafast intermolecular electron transfer dynamics: Perylene in electron-accepting micellar medium

The dynamics of ultrafast photoinduced intermolecular electron transfer (ET) from the excited singlet (S1) state of perylene (Pe) to an electron-accepting cationic surfactant molecule, N-cetylpyridinium chloride (CPC), in aqueous micellar solutions has been investigated using the femtosecond transient absorption spectroscopic technique with temporal resolution of 120 fs. The Pe molecule is localized at or near the micellar surface, where it coexists with the pyridinium moieties (headgroups of the micelle) of the surfactant molecule. Following photoexcitation of Pe, an electron is transferred to the neat and geometrically restricted headgroup of the micelle. Dynamics of the forward ET process as well as the geminate recombination or back ET (BET) process have been followed by monitoring the temporal evolution of the S1 state of Pe and the cation radical of Pe (Pe*+), respectively. The multiexponential forward ET process indicates that the ET dynamics is highly correlated with the spatial distributions of the micellar headgroups around a donor Pe molecule and thus dependent on the donor-acceptor distance. The distance-dependent ET and BET rates have been calculated following the method of Weidemaier and Fayer (J. Chem. Phys. 1995, 102, 3820) to get the best fit parameters for the multiexponetial temporal profiles for the S1 state of Pe as well as Pe*+. Because the acceptor is a constituent of the neat micellar medium, their confinement on the surface of the microheterogeneous medium provides a very large concentration such that, even though the forward transfer rate is 0.06 ps(-1) at the distance of closest approach, the ET process is complete within a 200-ps time domain. If the concepts of distribution of ET distances are utilized, the possible role of material diffusion on the kinetics of forward ET is ruled out. This is an experimental study to show, for the first time, the ultrafast distance-dependent light-induced ET dynamics following both the excited state of the donor and the cation radical formed in an ET process using the transient absorption spectroscopic technique in a self-reactive restrictive environment.     

肽链体系中的长程电子转移: 酪氨酸与色氨酸间电子转移的理论研究

用电子转移的半经典模型和量子化学半经验方法对色氨酸-酪氨酸二肽体系进行电子转移动力学参数计算.用AM1方法分别优化给体、受体和桥体几何构型,用线性反应坐标的构造了给体和受体分子间电子转移的双势阱,得到两透热势能面交叉处的反应坐标为R=(约等于)0.10,并确定了反应的内重组能及反应热.对色氨酰酪氨酸和酪氨酰色氨酸体系进行闭壳层HF自洽场计算,按Koopmans定理计算体系分子轨道分裂能值A(三角形),在R约为0处发现了A(三角形)的极小值,从而获得色氨酰酪氨酸及酪氨酰色氨酸体系分子内电子转移的电子转移矩阵元V~D~A分别为0.96kJ.mol^-^1和0.87kJ.mol^-^1.采用Marcus双球模型估算反应的溶剂重组能为64.60kJ.mol^-^1。     

Theoretical study of ultrafast heterogeneous electron transfer reactions at dye-semiconductor interfaces: coumarin 343 at titanium oxide

A theoretical study of photoinduced heterogeneous electron transfer in the dye-semiconductor system coumarin 343-TiO(2) is presented. The study is based on a generic model for heterogeneous electron transfer reactions, which takes into account the coupling of the electronic states to the nuclear degrees of freedom of coumarin 343 as well as to the surrounding solvent. The quantum dynamics of the electron injection process is simulated employing the recently proposed multilayer formulation of the multiconfiguration time-dependent Hartree method. The results reveal an ultrafast injection dynamics of the electron from the photoexcited donor state into the conduction band of the semiconductor. Furthermore, the mutual influence of electronic injection dynamics and nuclear motion is analyzed in some detail. The analysis shows that--depending on the time scale of nuclear motion--electronic vibrational coupling can result in electron transfer driven by coherent vibrational motion or vibrational motion induced by ultrafast electron transfer.     

Theoretical studies of electron and hydrogen transfer reactions between semiquinone radicals and oxygen

 To explore the interactions between ubiquinones and oxygen in living organisms, the thermodynamics of a series of electron and hydrogen transfer reactions between semiquinone radicals, as well as their corresponding protonated forms, and oxygen, singlet or triplet, were studied using the hybrid Hartree–Fock–density functional theory method Becke's three parameter hybrid method with the Lee, Yang, and Parr correlation functional. Effects of the solvent and of the isoprenyl tail on the electron and hydrogen transfer reactions were also investigated. It is found that semiquinone radicals (semiquinone anion radicals or protonated semiquinone radicals) cannot react with triplet oxygen to form the superoxide anion radical O₂ ⁻. In contrast, neutral quinones can scavenge O₂ ⁻ efficiently. In the gas phase, only protonated semiquinone radicals can react spontaneously with singlet oxygen to produce peroxyl radical (HO₂). However, both semiquinone anion radicals and protonated semiquinone radicals can react with singlet oxygen to produce harmful oxygen radicals (O₂ ^{− a l l b u l l} and HO₂, respectively) in aqueous and protein environments. The free-energy changes of the corresponding reactions obtained for different ubiquinone systems are very similar. It clearly shows that the isoprenyl tail does not influence the electron and hydrogen transfer reactions between semiquinone radicals and oxygen significantly. Results of electron affinities, vertical ionization potentials, and proton affinities also show that the isoprenyl tail has no substantial effect on the electronic properties of ubiquinones. Received: 3 July 2000 / Accepted: 6 September 2000 / Published online: 21 December 2000     

Syntheses and spectroscopic studies of spirobifluorene-bridged bipolar systems; photoinduced electron transfer reactions

Some 9,9'-spirobifluorene-bridged bipolar systems 1-3 containing 1,3,4-oxadiazole-conjugated oligoaryl and triarylamine moieties have been synthesized, in which 1 exhibits remarkable solvent-polarity dependent fluorescence properties due to a highly efficient photoinduced electron transfer reaction.     

Ultrafast quenching of tryptophan fluorescence in proteins: Interresidue and intrahelical electron transfer

Quenching of tryptophan fluorescence in proteins has been critical to the understanding of protein dynamics and enzyme reactions using tryptophan as a molecular optical probe. We report here our systematic examinations of potential quenching residues with more than 40 proteins. With site-directed mutation, we placed tryptophan to desired positions or altered its neighboring residues to screen quenching groups among 20 amino acid residues and of peptide backbones. With femtosecond resolution, we observed the ultrafast quenching dynamics within 100 ps and identified two ultrafast quenching groups, the carbonyl- and sulfur-containing residues. The former is glutamine and glutamate residues and the later is disulfide bond and cysteine residue. The quenching by the peptide-bond carbonyl group as well as other potential residues mostly occurs in longer than 100 ps. These ultrafast quenching dynamics occur at van der Waals distances through intraprotein electron transfer with high directionality. Following optimal molecular orbital overlap, electron jumps from the benzene ring of the indole moiety in a vertical orientation to the LUMO of acceptor quenching residues. Molecular dynamics simulations were invoked to elucidate various correlations of quenching dynamics with separation distances, relative orientations, local fluctuations and reaction heterogeneity. These unique ultrafast quenching pairs, as recently found to extensively occur in high-resolution protein structures, may have significant biological implications.     

Photoinduced electron transfer reactions by SmI2 in THF: luminescence quenching studies and mechanistic investigations

Photoluminescence quenching studies of SmI2 in dry THF were carried out in the presence of five different classes of compounds: ketone, alkyl chloride, nitrile, alkene and imine. The free energy change (DeltaG0) of the photoinduced electron transfer (PET) reactions was calculated from the redox potentials of the donor (SmI2) and acceptors. The bimolecular quenching constants (k(q)) derived from the Stern-Volmer experiments parallel the free energy changes of the PET processes. The observed quenching constants were compared with the theoretically derived electron transfer rate constants (k(et)) from Marcus theory and found to be in good agreement when a value of lambda = 167 kJ mol(-1) (40 kcal mol(-1)) was used for the reorganization energy of the system. A careful comparison of the excited state dynamics of SmII in the solid state to the results obtained in solution (THF) provides new insight in to the excited states of SmII in THF. The activation parameters determined for the PET reactions in SmI2/1-chlorobutane system are consistent with a less ordered transition state and high degree of bond reorganization in the activated complex compared to similar ground state reactions. Irradiation studies clearly show that SmI2 acts as a better reductant in the excited state and provides an alternative pathway for rate enhancement in known and novel functional group reductions.     

Ultrafast and ultraslow oxygen atom transfer reactions between late metal centers

Oxotrimesityliridium(V), (mes)3Ir=O (mes = 2,4,6-trimethylphenyl), and trimesityliridium(III), (mes)3Ir, undergo extremely rapid degenerate intermetal oxygen atom transfer at room temperature. At low temperatures, the two complexes conproportionate to form (mes)3Ir-O-Ir(mes)3, the 2,6-dimethylphenyl analogue of which has been characterized crystallographically. Variable-temperature NMR measurements of the rate of dissociation of the mu-oxo dimer combined with measurements of the conproportionation equilibrium by low-temperature optical spectroscopy indicate that oxygen atom exchange between iridium(V) and iridium(III) occurs with a rate constant, extrapolated to 20 degrees C, of 5 x 107 M-1 s-1. The oxotris(imido)osmium(VIII) complex (ArN)3Os=O (Ar = 2,6-diisopropylphenyl) also undergoes degenerate intermetal atom transfer to its deoxy partner, (ArN)3Os. However, despite the fact that its metal-oxygen bond strength and reactivity toward triphenylphosphine are nearly identical to those of (mes)3Ir=O, the osmium complex (ArN)3Os=O transfers its oxygen atom 12 orders of magnitude more slowly to (ArN)3Os than (mes)3Ir=O does to (mes)3Ir (kOsOs = 1.8 x 10-5 M-1 s-1 at 20 degrees C). Iridium-osmium cross-exchange takes place at an intermediate rate, in quantitative agreement with a Marcus-type cross relation. The enormous difference between the iridium-iridium and osmium-osmium exchange rates can be rationalized by an analogue of the inner-sphere reorganization energy. Both Ir(III) and Ir(V) are pyramidal and can form pyramidal iridium(IV) with little energetic cost in an orbitally allowed linear approach. Conversely, pyramidalization of the planar tris(imido)osmium(VI) fragment requires placing a pair of electrons in an antibonding orbital. The unique propensity of (mes)3Ir=O to undergo intermetal oxygen atom transfer allows it to serve as an activator of dioxygen in cocatalyzed oxidations, for example, acting with osmium tetroxide to catalyze the aerobic dihydroxylation of monosubstituted olefins and selective oxidation of allyl and benzyl alcohols.     

Ultrafast energy delocalization and electron transfer dynamics in 2-aminopurine-containing trinucleotides

The fate of electronically excited states in DNA base stacks is of tremendous importance for subsequent photochemical damage reactions in the genome. In this study we present a femtosecond broadband pump-probe study on the adenine isomer 2-aminopurine (Ap) incorporated into trinucleotides. After selective excitation of Ap we can monitor energy delocalization between neighboring Ap moieties as well as excited state electron transfer, depending on the sequence of the trinucleotide. Our results establish the time scale for intrastand excimer formation and reveal the lifetime of the excimer state.     

Monte Carlo simulations of heterogeneous electron transfer: New challenges

We report results of MC simulations of electron transfer across a metal electrode/electrolyte solution interface. The model presumes the Landau–Zener theory and a random walk on a two-dimensional lattice formed by crossing parabolic reaction free energy surfaces along the solvent coordinate. Emphasis is put on investigating the activationless discharge regime; the bridge-assisted electron transfer is also partially addressed. We have calculated effective electronic transmission coefficient as a function of the electrode overpotential and temperature in a wide range of orbital overlap. The dependence of the transmission coefficient on the electronic density of states is analyzed as well.