Mechanism for resonant O electron stimulated desorption from condensed O2. Non-adiabatic transitions and dynamics

Absolute kinetic energy distributions and yields associated with ground state ³P and excited state ¹D oxygen atoms have been obtained for O⁻ anion electron stimulated desorption from condensed O₂ in the electron energy range 6–15 eV. The observed yields are understood as resulting essentially from dissociative electron attachment reactions via the two lowest ²Σ⁺_g O⁻₂ resonance states through adiabatic and non-adiabatic transitions to the limits O⁻(²P) + O(³P) and O⁻(²P) + O(¹D). The kinetic energy distributions show the prominent role of electron multiple collision processes and post-dissociation interactions of the O⁻ anions in the condensed phase.     

Quenching of the dissociative electron attachment resonances of O2 physisorbed on amorphous ice

Measurements of electron stimulated desorption (ESD) yields of O⁻, at incident electron energies below 20 eV, from 0.15 monolayers (ML) of O₂ physisorbed at 20 K on a variety of molecular solids have been performed. It is observed that for O₂ condensed on 4 ML of H₂O, the O⁻ signal from dissociative electron attachment (DEA) to O₂ is entirely absent. We attribute this to a complete quenching of the dissociative ²Π_u, ²Σ⁺_g, and ²Σ⁺_u, resonances of O⁻₂ by the adjacent water molecules.     

Superoxide ion formation process on reduced MoO3---TiO2

Two novel Mo⁵⁺ ions, different from either the D_2d symmetry Mo⁵⁺ on anatase or the D_2hMo⁵⁺ on rutile, appeared on partially reduced molybdenum oxide supported on -titanic acid. The oxygen molecule is held on one of these novel Mo⁵⁺ ions but is not reduced to the superoxide ion. Oxygen is reduced to O⁻₂ entirely by the Mo⁴⁺ ion formed from the D_2d symmetry ion and the O⁻₂ is subsequently stabilized after moving to a Ti⁴⁺-site.     

Classical trajectory calculation for ion-pair formation in K+O2 collisions

Three-dimensional trajectory surface hopping calculations were performed on two diabatic energy surfaces. The covalent surface describes the K(²S) + O₂(³Σ⁻_g) state and the ionic surface K⁺(¹S) + O⁻₂(²Π_g). Transitions from one surface to another were computed through the Landau—Zener model. At small deflection angles, the energy loss distribution exhibits two peaks, as observed, due to O⁻₂ in its electronic ground state and to vibrationally excited O⁻₂.     

Role of axial ligand on the electronic structures of active intermediates in cytochrome P-450, peroxidase and catalase

DFT method (B3LYP) with 6-31G^* basis set was utilized in the computation of a fully optimized structure, net atomic charges and spin densities of the intermediate of cytochrome P-450-oxoiron(IV) porphyrin cation radical, compound I – in the presence of axial ligand such as thiolate (SMe⁻) imidazole (IM), phenoxide (OPh⁻), methoxide (OMe⁻) and chloride (Cl⁻). The results show doublet states in compound I are about 2–4 kcal/mol more stable than quartet states for all aforementioned ligands, and the doublet state is the ground state in all cases. However, electron donor ability of the ligands are in the order of SMe⁻ > IM > OMe⁻ > OPh⁻ > Cl⁻. Also the active oxidant intermediate of cytochrome P-450 between different mesomeric structures select sulfur oxygen radical type structure and can be viewed as (RS^↓)Fe^↑(IV)(O^↑)(Por). In horseraddish peroxidase (HRP) and peroxidase with histidine axial ligand π cation radical character of porphyrin ring is preferred (Im)Fe^↑(IV)(O^↑)(Por^↓). For the ligands such as OMe⁻, OPh⁻ and Cl⁻ oxidation mainly took place on the iron and the active intermediate can be viewed as (L)Fe^↑(V)(O)(Por) with one unpaired electron localized on the iron.     

Standard enthalpies of formation of Sr2CuO3 and Ca2CuO3

The enthalpies of reactions between alkaline-earth cuprates M₂CuO₃ (M = Ca, Sr) and hydrochloric acid were measured in a hermetic swinging calorimeter at 298.15 K. The M₂CuO₃ samples were prepared by solid-phase synthesis from calcium or strontium carbonate and copper oxide and characterized by X-ray powder diffraction, EDX and wet analysis. The standard enthalpies of formation obtained for the cuprates, −1431 ± 4 kJ mol⁻¹ for Ca₂CuO₃ and −1374 ± 3 kJ mol⁻¹ for Sr₂CuO₃, are discussed and compared with previous experimental and assessed values.     

Interaction of the E(D) state of Co with a jahn-teller active mode in [N(CH3)4]2CoCl4

The transition ⁴A₂ → ²E of Co²⁺ has been investigated in [N(CH₃)₄]₂CoCl₄ using optical absorption and magnetic circular dichroism. Three groups of lines with 274 cm⁻¹ progressions were observed. The structure of the spectra indicates a J-T interaction in the ²E state with strong depression of the frequency of the J-T active mode. The ground-state splitting is 7.2 cm⁻¹.     

Kinetic investigation of electronic energy transfer processes following the pulsed dye-laser generation of excited atomic barium, Ba[6s6p(P1)], in the presence of atomic strontium

The collisional behaviour of Ba[6s5d(³D_J)], 1.151 eV above the 6s²(¹S₀) electronic ground state, in the presence of atomic strontium, has been investigated in the ‘long-time domain' (ca. 100 μs–1 ms) following the pulsed dye-laser excitation of barium vapour at elevated temperature at λ = 553.5 nm (Ba[6s6p(¹P₁)] ← Ba[6s²(¹S₀)]. Ba(³D_J) is subsequently produced from the short-lived ¹P₁ state (τ_e = 8.37 ± 0.38 ns) by a number of radiative and collisional processes. It may then be monitored in the ‘long-time domain' by atomic spectroscopic marker methods involving either collisional activation of Ba(³D_J) by Ba(¹S₀) and He buffer gas to yield Ba[6s6p(³P_J)] with subsequent emission from the ³P₁ state (τ_e = 1.2 ± 0.1 μs): Ba[6s6p(³P₁)] → Ba[6s²(¹S₀)] + hv (λ = 791.1 nm). Alternatively, emission from Ba(¹P₁) may be monitored at long times following the generation of this short-lived state by energy pooling following self-annihilation of Ba(³D_J) + Ba(³D_J) from Ba[6s6p(¹P₁)] → Ba[6s²(¹S₀)] + hv (λ = 553.5 nm). The generation of Ba(³D_J) in the presence of atomic strontium yields emission in the long-time domain from Sr[5s5p(³P₁)] (τ_e = 19.6 μs): Sr[5s5p(³P₁)] → Sr[5s²(¹S₀)]  + hv (λ = 689.3 nm). Whilst the decay profiles at short times are complex in form, at long times all these atomic profiles show first-order kinetic removal with the decay coefficients for λ = 791.1 nm, 689.3 nm and 553.5 nm emissions in the ratio 1 : 2 : 2, consistent with overall third-order activation of the form: Ba(³D_J) + Ba(³D_J) + Sr(¹S₀) → Sr(³P_J) + 2Ba(¹S₀). The mechanism is modelled in detail, including measurement of integrated emission intensities, yielding kinetic data for fundamental collisional processes. The overall rate constant for the third-order collisional activation of Sr[5s5p(³P_J])from 2Ba[6s5d(³D_J)] + Sr[5s²(¹S₀)] takes the upper limit of 5.8 × 10⁻²⁷ cm⁶ atom⁻² s⁻¹ (T = 900 K). The rate constant for the two body collisional quenching of Ba[6s5d(³D_J)] by ground state atomic strontium, Sr[5s²(¹S₀)], is found to be (2.0 ± 0.1) × 10⁻¹² cm³ atom⁻¹ s⁻¹ (T = 900 K).     

Mass spectrometry investigation of the degradation of polyethylene terephtalate induced by low-energy (<100 eV) electrons

Polyethylene terephtalate (PET) thin films were damaged by low-energy (0–100 eV) electron irradiation to simulate the degradation of this polymer in electronic devices. The products formed were analyzed by mass spectrometry. The emission of anions from the polymer surface is associated with dissociative electron attachment (DEA) and dipolar dissociation (DD) for H⁻, and with DD for O⁻. The monotonic emission rise in O⁻ desorption as a function of incident electron energy is produced by mid-chain C–O–C cleavage, leading to chain scission. The signal of the positive mass fragments showed only a monotonic increase with electron energy. In this case, chemical recombination with hydrogen atoms also leads to chain scission.     

Electronic absorption spectrum of Ba(MnO4)2·3H2O/Ba(ClO4)2·3H2O

Polarized absorption spectra of Ba(MnO₄)₂·3H₂O/Ba(ClO₄)₂·3H₂O mixed single crystals are reported at 4.2°K. Previous ¹T₂ → ¹A₁ assignments for the 5200 Å and 3000 Å absorption bands of MnO₄⁻ are substantiated; further support is provided for the ¹T₁ → ¹A₁ assignment of the 3600 Å absorption band of MnO₄⁻. The site-splitting of the 5200 Å ¹T₂ state is E(¹E)−E(¹A) ≈ −150 cm⁻¹; that of the 3000 Å ¹T₂ state is E(¹E)−E(¹A) ≈ 300 cm⁻¹. A significant e vibronic intensity component is observed in the 5200 Å ¹T₂ state.     

Experimental and theoretical investigations on the electric field gradient at the Br site in Sr(BrO3)2 · H2O and Ba(BrO3)2 · H2O

Single-crystal Zeeman effect studies have been done using ⁷⁹Br NQR in Sr(BrO₃)₂ · H₂O and Ba(BrO₃)₂ · H₂O and the electric field gradient (EFG) parameters at the Br site have been determined. The point-charge model for the evaluation of EFG at the Br site, when applied to these systems, has not yielded satisfactory results. In another model, the total EFG is obtained as the sum of the covalent contribution and the inter-ionic contribution. To obtain the covalent contribution CNDO/2 MO calculations have been done for the (BrO₃)⁻ ions of these systems. There is excellent agreement with the experimental values in the case of Sr(BrO₃)₂ · H₂O, while the results on Ba(BrO₃)₂ · H₂O indicate that the structural data on this crystal need refinement.     

Synthesis and low temperature fluorination of the alkaline-earth palladates Ba2−xSrxPdO3 (x = 0–2)

Since the discovery of superconductivity in Sr₂CuO₂F_2+δ there has been an increased interest in ternary oxide-fluorides. Sr₂CuO₂F_2+δ is prepared via low temperature (T = 220 °C) reaction routes. Low temperature fluorination induces an interesting structural rearrangement in the parent compound Sr₂CuO₃, which is a one-dimensional material containing linear chains of vertex sharing CuO₄ squares along the crystallographic b axis. Upon fluorination, one oxide is substituted by two fluorides and Cu²⁺ becomes octahedrally coordinated by four oxides and two fluorides. The fluorinated compound Sr₂CuO₂F_2+δ displays the T-type structure (La₂CuO₄). Insertion of excess fluorine, δ, also takes place and this fluorine occupies interstitial sites in the T structure. Although the starting material Ca₂CuO₃ is isostructural to Sr₂CuO₃, Ca₂CuO₂F_2+δ displays the T′ (Nd₂CuO₄) structure due to the smaller radius of Ca²⁺ compared to that of Sr²⁺.

The alkaline-earth palladates with the general formula A₂PdO₃ (A = Ba, Sr) are isostructural with the A₂CuO₃(A = Ca, Sr) materials. We prepared the Ba_2−xSr_xPdO₃ (x = 0–2) series and performed low temperature fluorination, which led to the synthesis of the series Ba_2−xSr_xPdO₂F_2+δ (0 ≤ x ≤ 1.5). All the compounds in the Ba_2−xSr_xPdO₂F_2+δ series show T′ structure (Ca₂CuO₂F_2+δ). Similarities and differences with Sr₂CuO₂F_2+δ and Ca₂CuO₂F_2+δ will be discussed.     

Synthesis and crystal structure of the double barium-titanium methoxide [Ba2Ti4O(OMe)18(MeOH)7]·MeOH

The X-ray diffraction study of crystals isolated from solutions obtained by reaction of Ba(OMe)₂ with Ti(OMe)₄ (molar ratio 1:2) in methyl alcohol was carried out; the crystals of the methanol solvate of the double barium-titanium methoxide, [Ba₂Ti₄O(OMe)₁₈(MeOH)₇]·MeOH (1), contain two Ba²⁺ cations with different environments and two kinds of anionic binuclear titanium complexes with and without oxo-ligand, and thus can be formulated as [Ba(MeOH)₂]²⁺[Ba(MeOH)₅]²⁺[Ti₂O(OMe)₈]²⁻[Ti₂(OMe)₁₀]²⁻·MeOH.     

Electronic and vibronic dipole moments of CH2D

Isotopic substitution of a hydrogen atom by deuterium turns a non-polar ion such as CH₃⁻ into a non-centrosymmetric system, CH₂D⁻, suitable for rotational spectra detection in space. The vibrational contribution to the dipole moment of the ion is investigated in this paper. The electronic potential surface has been obtained in a first-order CI, starting from a full valence active space built by using projected localized orbitals, to which core valence correlation effects have been added to account for rehybridization. The vibrational functions are obtained in a basis of harmonic oscillators. Three levels of vibrational treatment are presented, i.e. harmonic, non-coupled and coupled modes. The final result for the transition moment in the lowest vibrational level, μ_v = 0.327 Debye, shows that CH₂D⁻ should be observed and may be a useful tracer of CH₃⁺ in interstellar chemistry.     

Synthesis and enthalpy of formation of SrB4O7·3H2O

Hydrated strontium borate, SrB₄O₇·3H₂O, has been synthesized and characterized by XRD, FT-IR, DTA-TG and chemical analysis. The molar enthalpy of solution of SrB₄O₇·3H₂O in 1 mol dm⁻³ HCl(aq) was measured to be (21.15 ± 0.29) kJ mol⁻¹. With incorporation of the previously determined enthalpies of solution of Sr(OH)₂·8H₂O(s) in [HCl(aq) + H₃BO₃(aq)] and H₃BO₃ in HCl(aq), and the enthalpies of formation of H₂O(l), Sr(OH)₂·8H₂O(s) and H₃BO₃(s), the enthalpy of formation of SrB₄O₇·3H₂O was found to be −(4286.7 ± 3.3) kJ mol⁻¹.     

Two-component density functional theory of positron binding to negative ions

The problem of binding in positron-negative ion systems has been addressed via two-component density functional theory. Calculations have been performed within the local density approximation for electron exchange-correlation as well as for the electron-positron correlation potential using a self-interaction corrected version of the density functional equations. Our results indicate that a positron forms a stable bound state with the negative ions Li⁻,B⁻,C⁻,O⁻,F⁻ and Cl⁻ with respect to dissociation into a negative ion and a positron or a neutral atom and positronium. Inclusion of electron-positron correlation deepens the positron bound state and stabilizes the system compared to earlier exchange-only calculations.     

Reactions of cyclo-(t-Bu4Sb4) with alkali metals; syntheses and crystal structures of [M(L)n(t-Bu4Sb3)] (M=Na, K; n=1, 2) and [K(L)(t-Bu3Sb2)] (L=(Me2NCH2CH2)2NMe)

Reduction of cyclo-(t-Bu₄Sb₄) (1) with sodium or potassium in boiling tetrahydrofuran leads to the anions [t-Bu₄Sb₃]⁻ and [t-Bu₃Sb₂]⁻. Crystallization with pentamethyldiethylenetriamine (L) gives [M(L)_n(t-Bu₄Sb₃)] (n=1, M=Na (2), K (3); n=2, M=K (4)) and [K(L)(t-Bu₃Sb₂)] (5). Crystal structure analyses reveal coordination of the anionic antimony ligands on the alkali metal ions for 2, 3, and 5. In contrast, no Sb---K interactions were observed in the structure of 4.     

Synthesis and chemistry of the bis(trimethylsilyl)amido bis-tetrahydrofuranates of the group 2 metals magnesium, calcium, strontium and barium. X-ray crystal structures of Mg[N(SiMe3)2]2·2THF and related Mn[N(SiMe3)2]2·2THF

Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe₃)₂}₂, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe₃)₂]·THF and M[N(SiMe₃)₂]₂·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe₃)₂]₂·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me₃Si)₂NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH₂CH₂O)_nCH=CH₂ (n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from ¹H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol.     

Photodestruction of NO2 using time resolved multicoincidence detection photofragment spectroscopy

We present an experiment on the photodestruction of the NO₂⁻ anion at 266 nm. We have quantified the competition between photodetachment and photodissociation and have identified the nature of the photodissociation process from the photofragment angular distribution. This study involves a novel technique; time resolved multicoincident detection photofragment spectroscopy. A three-dimensional double exposure CCD camera is employed. The system provides the position (x,y) and the relative arrival time (t) of all fragments. In the case of photodissociation events, NO and O⁻ fragments are detected for each event. The detection of multiple events per laser shot is made possible by using center-of-mass selection.     

EPR lineshape studies of low-temperature vanadium 3d polaron dynamics in the 70V2O5-30P2O5 binary glass

In a specimen of 70V₂O₅-30P₂O₅glass, EPR lineshapes of the vanadium 3d¹ polaron have been studied between 4 and 77 K. At the lowest temperature the unpaired electron is localized at a single ⁵¹V site, and values of g=1.959, g= 1.989, A = 156.6 × 10⁻⁴ cm⁻¹ and A=53.8 × 10⁻⁴ cm⁻¹ have been measured. A Markovian small-step rotational diffusion model consistent with the random structure of the glass network is proposed for the polaron dynamics at the higher temperatures up to 77 K. This motion has a small activation energy barrier of 114 μeV.