Inner-shell excitation of formaldehyde,acetaldehyde and acetone studied by electron impact

Excitation and ionisation of the carbon and oxygen 1s electrons of formaldehyde, acetaldehyde and acetone have been examined by small-angle inelastic scattering of 2.5-keV electrons, with energy resolutions in the range 0.20–0.50 eV FWHM. Features in the electron energy loss spectra below the inner-shell ionisation thresholds have been assigned to transitions to unoccupied valence (π*) and Rydberg orbitals. Broad maxima in the inner-shell continua of all three molecules have been interpreted as resonances associated with transitions to σ*(CO) orbitals. The assignments of the acetaldehyde and acetone spectra have been supported by comparison with those for CH₄ and H₂ CO. The adiabatic first ionisation potential of H₂ NO and H₂ CF have been estimated from the inner-shell spectra of formaldehyde using the equivalent-core analogy.     

Vibrational control of molecular electron transfer reactions

ABSTRACT

Vibrational motions promote molecular electron transfer (ET) reactions by bringing electron donor and electron acceptor electronic states to fleeting resonance, and by modulating the donor-to-acceptor electronic coupling. The main experimental signature of molecular motion effects on the ET rate is the temperature dependence of the rate, which gives information about the overall free energy activation barrier for the ET reaction. Another approach to probing the vibrational control of ET reactions is to excite specific electron-transfer-active vibrational motions by external infrared (IR) fields. This type of experimental probe is potentially more specific than thermal excitation and recent experiments have shown that molecular ET rates can be perturbed by mode-specific IR driving. We review the theory and experiments of vibrational control of ET rates, and discuss future challenges that need to be tackled in order to achieve the mode-specific tuning of rates.     

Single and double ionization of neon 2s- and 2p-subshells by proton and electron impact

Absolute single and double ionization cross sections of neon 2s- and 2p-subshells for proton (40–900 keV) and electron impact (0.2–10 keV) have been measured using photon spectroscopy in the spectral range of the vacuum ultraviolet. Cross sections for double ionization decrease more rapidly with increasing impact energy than cross sections for single ionization. No definite asymptotic energy dependence of a Bethe-Fano-plot could be found for double ionization in contrast to single ionization. The experimental results are compared with theoretical predictions of the shake-off model and Gryzinski's classical binary encounter theory. Better agreement is found with the latter, indicating that successive binary collisions have to be considered as a strong mechanism for double ionization by protons or electrons of the investigated energy range. Comparison is made with other experimental results for double ionization by photon impact or capture ionization by proton impact.     

Intramolecular electron scattering and electron transfer following autoionization in dissociating molecules

Resonant Auger decay of core-excited molecules during ultrafast dissociation leads to a Doppler shift of the emitted electrons depending on the direction of the electron emission relative to the dissociation axis. We have investigated this process by angle-resolved electron-fragment ion coincidence spectroscopy. Electron energy spectra for selected emission angles for the electron relative to the molecular axis reveal the occurrence of intermolecular electron scattering and electron transfer following the primary emission. These processes amount to approximately 25% of the resonant atomic Auger intensity emitted in the studied transition.     

Nonequilibrium dynamics of correlated electron transfer in molecular chains

The relaxation dynamics of correlated electron transport along molecular chains is studied based on a substantially improved numerically exact path integral Monte Carlo approach. As an archetypical model, we consider a Hubbard chain containing two interacting electrons coupled to a bosonic bath. For this generalization of the ubiquitous spin-boson model, non-Boltzmann equilibrium distributions are found for many-body states. By mapping the multiparticle dynamics onto an isomorphic single particle motion, this phenomenon is shown to be sensitive to particle statistics and, due to its robustness, allows for new control schemes in designed quantum aggregates.     

The threshold electron impact spectrum of molecular oxygen

The threshold electron impact spectrum of molecular oxygen has been studied using a high energy resolution electron spectrometer in the energy region 2-15.2 eV and the penetrating field method for scattered electrons. The measured features such as core excited resonances as well as Rydberg and valence states are measured in threshold and metastable spectra. They are identified and assigned according to their energy positions, energy spacing between vibrational levels and compared with similar data from the literature. A good agreement was found in the energy positions between measured features and corresponding potential energy diagram for Rydberg states for molecular oxygen given by Morrill et al. [1].Received: 13 January 2004, Published online: 20 April 2004PACS: 34.80.Gs Molecular excitation and ionization by electron impact     

2D-Conductivity of thin Pd films condensed at low temperatures

Resistance measurements have been made on quenched condensed Pd films with thicknesses between 25 Å and 350Å. The films are prepared under different evaporation conditions by varying the system pressure between 10^?8 and 10^?5 mbar. Resistance minima with a logarithmic increase of the sheet resistance are observed for thick films (d<350Å) condensed under intentionally “bad” (10^?5 mbar) vacuum conditions, as well as for thin films (d<50Å) condensed at pressures around 10^?8 mbar. Structure investigations show that the thick films are granular. For these films the relation of granularity to 2D localization is discussed. The thin films are continuous and the logarithmic resistance increase is in agreement with predictions of 2D-theories.     

Vibrational excitation by electron impact in thin solid films of cyclopropane

Vibrational electron-energy-loss spectra of solid films of cyclopropane have been recorded at different incident energies, scattering angles, and upon changing the sample crystallinity. The intensity variations are exploited for the assignment of the observed vibrational modes. A simple model is used to explain the intensity distribution in the multiple scattering spectral region dominated by twofold loss processes. This model demonstrates that dipole scattering processes may be distinguished from excitation through impact scattering even in completely disordered samples by comparing the intensities of the multiple scattering bands to those of the fundamental vibrations.     

EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Charge transfer in mixed proton, oxygen ion and electron solid oxide conductor

Analysis of the equivalent scheme of the mixed proton-oxygen ion-electron conductor (MPOEC) allowed to obtain relationships between parameters of the membrane (total conductivity and transfer numbers) and parameters of the charge and mass transfer through the membrane (partial ion and electron currents, the specific flux of hydrogen at the cathode membrane surface) under regime of electrochemical reforming. It was stated that presence of proton conductivity in addition to oxygen ion conductivity led to increase of total flux of produced hydrogen. However, under conditions typical for the electrochemical reforming of methane into hydrogen, the specific hydrogen flux is about four times lower in the case when the membrane has proton-electron conductivity than in the case when the membrane has oxygen ion-electron conductivity. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment

The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a π^* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the standard Watson-Crick pairing scheme. Received 6 April 2002 Published online 13 September 2002     

Photoinduced energy transfer in blend films of hole and electron transport materials

The photoluminescence properties of the blend films consisting of the hole transport and electron transport materials, PVK and Alq₃, are studied by steady-state and time-resolved photoluminescence (PL) spectroscopy. Both the relative intensity and the photoluminescence lifetime are intensively dependent of the weight ratios of PVK and Alq₃. The detailed analysis of experiment data provides clear evidence for a Förster energy transfer from excited PVK, as donor, to Alq₃, as acceptor, based on nonradiative resonant transfer mechanism, and allows the determination of Förster radius and the concentration dependent energy transfer efficiency.     

Intra- and intermolecular proton transfer in methyl-2-hydroxynicotinate

Spectral characteristics of methyl 2-hydroxynicotinate (MEHNA) have been studied using absorption, fluorescence excitation and fluorescence spectroscopy, as well as, using single photon counting nanosecond spectrofluorimeter. MEHNA is present as enol in less polar solvents and keto in polar media. In non-polar solvents, large Stokes shifted fluorescence band is assigned to phototautomer, formed by excited state intramolecular proton transfer (ESIPT), whereas fluorescence is only observed from keto form in polar solvents. In aqueous and polar solvents monocation (MC) is formed by protonating the exo carbonyl oxygen atom in the ground state (S₀) and in the first excited singlet state (S₁), MC is obtained by protonating carbonyl oxygen atom of the ester. It is formed by ESIPT from exo carbonyl proton to carbonyl oxygen atom of the ester. Dication is formed by protonating both the oxygen atoms. Two kinds of monoanions formed by deprotonating phenolic proton or >N-H proton of keto suggest the presence of enol and keto in aqueous solution. In cyclohexane MC is formed by protonating carbonyl oxygen in both S₀ and S₁ states. The electronic structure calculations were performed on each species using semi-empirical quantum mechanical AM1 method and density functional theory B3LYP with 6-31G^** basis set using Gaussian 98 program, along with potential energy mapping, to characterize the particular species.     

Evolution of optical properties and molecular structure of PCBM films under proton irradiation

Low-energy proton irradiation effects on the optical properties and the molecular structure of phenyl-C₆₁-butyric acid methyl ester (PCBM) are studied in this work. The PCBM films are irradiated by 100-keV proton beams with fluences of 5×10¹² p/cm², 5×10¹³ p/cm², and 5×10¹⁴ p/cm², respectively. The photoluminescence (PL) peaks of the post-irradiated PCBM films show a progressive decrease in the peak intensity as the proton fluences increase, which can be attributed to the deep defect levels induced by proton irradiation. Additionally, a slight blue-shift in the PL spectrum is also observed at a proton fluence of 5×10¹⁴ p/cm². The underlying mechanism can be traced back to the lift of the lowest unoccupied molecular orbital (LUMO) level, which is caused by the attachment of methoxy radicals on ortho position of the phenyl ring in the post-irradiated PCBM structure. This work is of significance in understanding the radiation hardness and the damage mechanism of the PCBM film in radiation environments, which is essential before it is put into practical application in space.