Photoinduced intramolecular electron-transfer reactions in carbazole-fullerene and phenothiazine-fullerene linked compounds in benzene and benzonitrile as studied by fluorescence, transient absorption, time-resolved EPR, and magnetic field effects

Photoinduced intramolecular electron-transfer reactions in carbazole (Cz)-fullerene (C₆₀) (Cz(8)C₆₀) and phenothiazine (Ph)-C₆₀ (Ph(n)C₆₀ (n=8, 10, 12)) linked compounds have been investigated in benzene and benzonitrile by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance measurements, and by magnetic field effects on the decay rate constants of the photogenerated biradicals. In benzonitrile, photoinduced intramolecular electron transfer from Cz to the singlet excited state of C₆₀ (¹C₆₀ ^*) occurred in Cz(8)C₆₀, but not to the triplet excited state (³C₆₀ ^*), while the intramolecular electron-transfer to both¹C₆₀ ^* and³C₆₀ ^* occurred in Ph(n)C₆₀ (n=8, 10, 12). In benzene, on the other hand, no electron transfer to both¹C₆₀ ^* and³C₆₀ ^* took place in all linked compounds. These results were interpreted in terms of the different Gibbs free energy changes in the two solvents.     

Structures and electronic states of photoexcited states in a system of two nitroxide radicals linked to fullerene studied by two-dimensional pulsed nutation and time-resolved electron paramagnetic resonance spectroscopy

Magnetic properties of fulleropyrrolidine adducts with two stable nitroxide radicals (2,2,6,6-tetramethylpiperidine-1-oxyl, TEMPO) were studied in toluene solution by continuous-wave time-resolved (TR) and pulsed electron paramagnetic resonance (EPR) spectroscopy in the ground and photoexcited states. Four isomers of the bisadduct,trans-1,trans-2,trans-3, and equatorial forms, having the second pyrrolidine ring at different [6-6] bonds were synthesized. In the ground states, the exchange interaction between two TEMPOs is so small that the spin state of the bisadduct is a doublet in nature. By means of spectral simulations of the EPR spectra in frozen solution at 70 K, the upper limit of the exchange interaction was estimated to be 5 MHz for thetrans-1 andtrans-2 and 10 MHz for thetrans-3 and equatorial isomers. The simulation was also made to determine relative positions of the two TEMPO groups with respect to the pyrrolidine ring. Photoexcited states of the bisadducts with excitation of the 532 nm laser pulse were studied in frozen toluene solution at 5–100 K by using two-dimensional (2-D) pulsed nutation EPR and TREPR. The spin multiplicity of the excited state was determined by the nutation frequency. All of the four bisadducts showed strong exchange couplings between two TEMPOs and fullerene triplet³C ₆₀ ^* , resulting in the generation of the excited quintet and triplet states. The excited triplet states have been observed and assigned for the first time in strongly coupled triplet-radical systems. The zero-field splittings of the quintet state determined from the 2-D nutation EPR spectra were analyzed as the sum of the spinspin interactions among the three paramagnetic centers, two TEMPOs and³C ₆₀ ^* . On the basis of these analyses, the spin distribution on the³C ₆₀ ^* part and the geometry of two TEMPOs are discussed.     

Metastable helium cluster He<Stack><Subscript>4</Subscript><Superscript>*</Superscript></Stack>

The existence of a metastable cluster He ₄ ^* with total spin S = 2 is predicted. The cluster consists of two covalently bound excited spin-polarized triplet He ₂ ^* molecules and is rectangular in shape. The electron wavefunctions, the dependence of the energy He ₄ ^* system on the distance between the He ₂ ^* triplet molecules, the atomic spacing, the frequency spectrum of natural oscillations of the cluster, and other characteristics are calculated from first principles. It is shown that the metastable state is formed if one of the excited He ₂ ^* molecules is in the ³Σ _u ⁺ state, while the other is in the ³Π_g state. The radiation lifetime τ of the metastable cluster He ₄ ^* is calculated; it is found to range from 100 to 200 s, which is much longer than the lifetime τ ≈ 20 s of the triplet molecule He ₂ ^* (³Σ _u ⁺ ). The height U ≈ 0.5 eV of the potential barrier preventing the departure from the local energy minimum is determined. The energy E_acc ≈ 9 eV/atom accumulated in the He ₄ ^* cluster is calculated; this energy considerably exceeds the energy of known chemical energy carriers. It is shown that the accumulated energy is released virtually completely during decomposition of the He ₄ ^* cluster into individual helium atoms. This means that helium clusters are a promising material with a high accumulated energy density (HEDM).     

Electron affinities of the bromine oxides BrOn,n = 1-4

Bromine oxides are of significant interest due to their importance in atmospheric chemistry. Density functional theory (DFT) methods have been used in conjunction with a DZP++ (double-ζ plus polarization with diffuse functions) basis set to study the molecular geometries and total energies of BrOn and BrO^- _n (n = 1-4). The adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert) of the bromine oxide and the vertical detachment energy (VDE) of each anion are reported. Harmonic vibrational frequencies and zero point energies are also reported. Five different DFT methods were employed for comparison. Among these, the BHLYP method predicts the geometries and the vibrational frequencies in best agreement with available experimental data, while the the other methods do better in predicting the limited number of energetic quantities determined observationally. The predicted adiabatic electron affinities are 2.38 eV (BrO, experiment 2.35 eV), 2.36 eV (BrO₂), 3.35 eV (BrOO), 4.32 eV (BrO₃), 2.91 eV (BrOOO) and 5.28 eV (BrO₄). The electronic ground state of BrOO^- is a triplet (³A^") state. Predicted Br–;O bond distances range from 1.61 (BrO₃) to more than 2 Å for Br...O₂ for the neutral molecules; and from 1.61 Å for BrO^- to 1.82 Å for BrO^- to more than 2 Å for Br^-...O₃ among the anions. The BrOO isomer (C_s symmetry) is predicted to lie 17–18 kcal mol^-1 below the C_2v symmetry OBrO structure. The asymmetric ³A^" anion BrOO^- analogously lies below OBrO^-, in this case by 40–41 kcalmol_-1. BrOOO (C_s symmetry) is predicted to lie 42-45 kcalmol-1 below the symmetric C_3v BrO structure. Finally the asymmetric BrOOO- anion (C₁ symmetry) is predicted to lie 10-13kcal mol-1 below symmetric C_3v BrO^- ₃.     

Electron spectroscopy with excited atoms and photons.: X. Halogen-substituted methanes and methyl amines

Electron binding energy spectra have been measured for CH₃Cl, CH₃Br, CH₃I, CFCl₃, CF₂Cl₂, CF₃Cl, CF₄, CH₃NH₂, (CH₃)₂ NH and (CH₃)₃N. Measurements have been made using 584 Å (21.22 eV) photons as well as with 2³S(19.82 eV) and 2¹S(20.62 eV) metastable helium atoms. Relative spectral intensities are compared for photoionization and Penning ionization.     

On the energy dependence of the yield of doubly charged negative ions during the capture of free electrons by C60(CF3)12 trifluoromethylfullerene molecules

Peaks of C₆₀(CF₃) _n ^2? doubly charged negative ions (n = 6–12) have been observed in the mass spectra of the resonance electron capture by trifluoromethylfullerene C₆₀(CF₃)₁₂ molecules. It has been established that these ions are formed owing to the attachment of two free isoenergetic electrons. The autodetachment of an extra electron has been detected for the doubly charged molecular ions (n = 12). It has been established from the observation of the delayed fragmentation of the most abundant ions with n = 8 and 10 that the doubly charged negative ions, like their singly charged analogs, are metastable with respect to the separation of the CF₃ fragment(s). The yield of doubly charged negative ions has been obtained as a function of the electron energy. By comparing them with the analogous dependences for the singly charged ions, the specific features have been revealed which were associated with the presence of the repulsive Coulomb barrier and the regular effect of the doubled energy of two additional electrons on the energy dependence of the dissociative decay of the doubly charged negative ions. The absolute cross section for the formation of the C₆₀(CF₃) ₁₀ ^2? ions has been measured. At the energy of their yield maximum near the 5 eV, it is ～1 × 10^?19 cm².     

Microwave spectrum,structure, and dipole moment of 7-oxabicyclo[2.2.1]heptane

The microwave spectrum of 7-oxabicyclo[2.2.1]heptane has been assigned in the ground and two excited vibrational states. Relative intensity measurements indicate that these two vibrations have wavenumbers of 120(30) and 330(30) cm^?1. The dipole moment obtained from Stark effect measurements is 1.621(10) D. The molecule is shown to have C_2v symmetry and the assignment of the two singly substituted ¹³C species gives the following skeletal structure: C₁-C₂ = 1.537(5) Å; C₂-C₃ = 1.551(5) Å; C₁-O = 1.452(10) Å; ?C₁OCC₄ = 95.3(10)° φ = 113.1(5)°.     

Excitation of bands of the first negative system of the N 2 + ion in collisions of N+ and O+ ions with N2 molecules

Absolute values of the excitation cross sections of the (0,0) bands [for O⁺(⁴ S), O⁺(² P)-N₂ pairs] and the (0,0), (0,1), (1,2), and (2,3) bands [for N⁺(³ P)-N₂ pairs] of the first negative system of the N ₂ ⁺ ion have been measured in collisions with nitrogen molecules of nitrogen and oxygen ions in the ground state and in a metastable state in the interval of ion energies 1–10 keV. The process of excitation of the (0,0) band of the first negative system of the N ₂ ⁺ ion by oxygen ions in the metastable ² P state is of a quasi-resonant character. The presence in the beam of ions in metastable states was monitored by measuring the excitation efficiency of the (0,0) band λ3914 Å of the N ₂ ⁺ ion in different operating regimes of the highfrequency ion source. For N⁺ ions in the ³ P ground state, as the collision frequency is decreased the relative vibrational population of the v′=1 and v′=2 levels of the B ²Σ _u ⁺ state of the N ₂ ⁺ ion is observed to deviate strongly from the value calculated in the Franck-Condon model.     

Polar smectic subphases: Phase diagrams, structures and X-ray scattering

We analyze a discrete phenomenological model accounting for phase transitions and structures of polar Smectic-C* liquid-crystalline phases. The model predicts a sequence of phases observed in experiment: antiferroelectric SmC _A ^* –ferrielectric SmC _FI1 ^* –antiferroelectric SmC _FI2 ^* (three-and four-layer periodic, respectively)–incommensurate SmC _α ^* –SmA. We find that, in the three-layer SmC _FI1 ^* structure, both the phase and the module of the order parameter (tilt angle) differ in smectic layers. This modulation of the tilt angle (and therefore of the layer spacing d) must lead to X-ray diffraction at the wave vectors Q _s =2πs/d(s=n±1/3) even for the nonresonant scattering.     

Solubility limit of impurities in silicon after laser induced melting

The solubility of several dopants (Sb, Ga, Bi, In) in laser treated silicon has been investigated. The dopants were introduced by vacuum deposition followed by ruby laser irradiation. Their solubility was determined by Rutherford backscattering spectroscopy measurements in channelling and random conditions. In all cases, a maximum solubilityC _S ^* , much higher than the equilibrium solubility limitC _S ⁰ and independent of the pulsed laser energy density, was found. The values obtained are in good agreement with those calculated from a simple model based on phase diagram considerations, using the relationship: $$C_S^* = \frac{{C_S^0 }}{{k_0 }}k^* ,$$ wherek ₀ andk ^* are the equilibrium and effective distribution coefficients. Finally, the existence of a new solubility limit for a laser treatment is discussed.     

Positronium interactions with gases in pores of silicagels

Positronium interaction with O₂, NO, Cl₂ molecules in pores of silicagels has been investigated by the methods of lifetime and angular correlation. For silicagel with diameter of pores ≈100 Å it was obtained that the rate constant of positronium conversion on oxygen was (2.4±0.2)10⁷ sec^?1 atm^?1 and on nitrogen oxide (2.6±0.2)10⁷ sec^?1 atm^?1. The rate constant of the positronium chemical reaction with Cl₂ was found to be ≈10^?11 sec^?1 atm^?1. The results of investigation of positronium interactions with oxygen in the gas phase, organic liquids, zeolites, liquid argon, and nitrogen are explained in terms of the formation of an excited complex PsO ₂ ^* . The decay of this complex to Ps and O₂ makes possible positronium conversion, and stabilization of the complex leads to annihilation in the bound state (chemical reaction). Study of positronium interaction with O₂ in silicagels (diameters of pores 100, 30 and 16 Å) confirms the assumption of the complex formation. The rates of chemical reaction and of conversion become equal for pores of diameter of 20 Å. The estimated lifetime of the PsO ₂ ^* complex is τ _k ? 10^?12 sec.     

Formation of doubly charged negative ions under the conditions of the resonant electron capture by fluorofullerenes

Doubly charged negative ions formed when electrons with controlled energies interact with isolated fluorinated fullerene molecules C₆₀F _n (n = 36, 48) have been detected and investigated by resonant electron capture mass spectrometry. The dependence of the intensity of the formation of doubly charged negative ions of fluorofullerenes on the energy of attached electrons has been measured. An original method, which is based on the experimental data and does not require additional calibration quantities, has been developed for estimating the absolute cross section for the formation of doubly charged negative ions. The absolute cross sections for the formation of the most intensely formed ions C₆₀F ₃₆ ^2? and C₆₀F ₄₈ ^2? are estimated to be about 1.1 × 10^?24 and 1.5 × 10^?24 m² at their maximum-yield energies of 2.0 and 1.6 eV, respectively.     

Energy transfer between Eu3+ ions in a lattice with two different crystallographic sites: Y2O3:Eu3+, Gd2O3:Eu3+ and Eu2O3

The Eu³⁺ ion occupies two different crystallographic sites in (Y_1−xEu_x)₂O₃ and (Gd_1−xEu_x)₂O₃, with site symmetry S₆ and C₂. Energy transfer over more than 7 Å occurs from Eu³⁺ (S₆) ions to Eu³⁺ (C₂) ions. This is shown to be a direct one-phonon assisted process, in combination with a one-site resonant two-phonon assisted process at higher temperatures. For x = 1 there is energy migration over the Eu³⁺ (C₂) sublattice to quenching impurities. The presence of cooperative absorption points to superexchange interaction between the Eu³⁺ ions.     

Photodesorption of O<Subscript>2</Subscript> from Ag<Subscript>2</Subscript><Superscript>-</Superscript>: A time-resolved study of Ag<Subscript>2</Subscript>O<Subscript>2</Subscript><Superscript>-</Superscript>

We present time-resolved photoelectron spectra of mass-selected Ag₂O₂ anions. The anions are photoexcited by photons with an energy of 3.1 eV, and photoelectron spectra of the excited species Ag₂O₂ ^{- *} and the subsequently appearing fragments are recorded using a probe laser pulse with a photon energy of 1.5 eV. The excited state of Ag₂O₂ ^- has a short lifetime of 130 fs±70 fs only and decays by direct photodesorption of O₂. The data demonstrate the ability of time-resolved photoelectron spectroscopy (TR-PES) to observe the breaking of chemical bonds if the decay process of the excited state is direct (non-thermal desorption). The data are compared to recent results of a NeNePo experiment [1] on the same system. PACS 68.43.Tj; 78.47.+p; 33.80.Eh; 36.40.-c     

Stoß-Depolarisation angeregter Neon-Atome

Variations of the number densities of excited Neon 2p ₄ and 3s ₂ levels were induced by interaction of a low pressure Ne or He-Ne discharge with the linearly polarized 633 nm light of a He-Ne gas laser. They are associated with partial alignment of those atoms having undergone a stimulated transition and consequently with anisotropy and polarization of the spontaneous radiation emitted by the discharge. From its gradual decrease at increasing pressure, depolarization cross sections ofQ _Ne*?Ne ^* =(157±12) Ų andQ _Ne*?He ^* =(63±7) Ų at mean relative velocity are derived. Comparison with values calculated by application of an adiabatic theory including sudden approximation yields good agreement in the case of Ne^*-He interaction and a discrepancy of 35% in the case of Ne^*-Ne interaction.     

Velocity dependence of the chemi-ionization of H2O and D2O on impact of 21S and 23S helium atoms

The velocity dependence for the ionization of H₂O and D₂O to form H₂O⁺ and D₂O⁺ in collisions with both 2³S and 2¹S metastable helium atoms has been measured in a crossed molecular beam apparatus using a mechanical velocity-selector on the metastable beam. The cross-sections are found to be proportional to the —n power of the relative collision energy, with n ? 0.4 for both metastable atoms in both gases. The branching ratios H₂O⁺/OH⁺ and D₂O⁺/OD⁺ were both found to be 4.3 for both metastable helium atoms, and to be independent of the relative collision energy.     

Quenching of excited strontium atomic state measured in H2- and CO-flames

The efficiency of resonance fluorescence, Y, of the strontium resonance line (¹P₁→¹S₀ transition) at 4607.33 Å was measured in CO/N₂O, CO/O₂/Ar, and H₂/O₂/CO₂/N₂ flames at atmospheric pressure. From these data, the specific quenching cross sections, σ_qu, for CO₂ and CO were found to be (60 ± 10) Ų and  (300 ± 60) Ų, respectively. The experimental cross sections were confronted with the intermediate ionic-state curve-crossing model and chemical quenching model, respectively.     

Hexavacancies in crystalline silicon

The kinetics of disorientation of B ₈₀ ⁴ centers is studied. The reorientation energy of the centers is determined to be ～1.5 eV. Based on the fact that this value is close to the energy of hexavacancy transition from the ground state to the first metastable state, it is concluded that the B ₈₀ ⁴ center is a ring hexavacancy. The reorientation mechanism is explained by the hexavacancy transition to the metastable state and, then, to a state with a new orientation.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Excitation of projectile Rydberg states in the collisions Be+-He and Mg+-He, 10–75 keV

The photoabsorption coefficient of molecular oxygen has been measured at 1215.70 Å and in the ranges 1205 Å–1214 Å and 1218 Å–1225 Å with an average resolution of ±0.015 Å. The light source in this experiment was the Doppler shifted radiation obtained from Stark quenching of a metastable hydrogen beam with energies between 2 keV and 60 keV. Using observation angles of 45°, 90°, and 135° with respect to the beam the above mentioned tuning ranges are obtained. Our data join smoothly to those of Ogawa [1] in the range 1214 Å–1218 Å and are in fair agreement with earlier measurements in other laboratories. Analytical expressions for the absorption coefficient for use in geophysical applications are presented for the whole wavelength range 1205 Å–1225 Å. Rotational structure of the absorption coefficient in the range 1220 Å–1223 Å arising from the 3-0 band of theα ¹ ∑ _u ⁺ -X ³ ∑ _g ^? forbidden transition in molecular oxygen is clearly resolved in the present measurements. A transition probability ofA=4×10⁴ s^?1 is obtained for this system. A careful study of a possible pressure dependence of the absorption coefficient was made. Except from the region were rotational line absorption occurs and the single point at 1215.70 Å no measurable effect was found for pressures below 100 Torr.