A kinetic study of proton transfer reactions of NH+4, CH3NH+3, and PH+4 with calcium atoms

Cross section measurements for the proton transfer reactions of NH⁺₄, CH₃NH⁺₃, and PH⁺₄ with Ca(g) have been obtained over a range of low ion kinetic energies. For all reactions studied the cross sections drop sharply with increase in ion kinetic energy, indicating exothermic behavior. The results show that Ca(g) is an unusually strong base with a proton affinity in excess of 9.2 eV. Cross sections for the PH⁺₄Ca reaction are an order to magnitude higher than those for the NH⁺₄Ca reaction for ion energies between one and three eV. This effect is not explained by simple theories of ion-induced dipole interactions. It is suggested that the enhanced rate of the PH⁺₄Ca reaction may be due to d-orbital participation.     

Complex formation in proton—D2 collisions

Classical trajectory calculations are used to compute the formation cross section (suitably defined) for strongly interacting collision complexes formed in H⁺ + D₂ collisions in the kinetic energy range from 0.1 to 4 eV. This cross section corresponds to the usual Langevin cross section only if the kinetic energy is less than 0.2 eV, and provided that little initial excitation is present, while for higher kinetic energies it drops exponentially. It is in much better agreement with absolute integral cross sections observed experimentally than the latter. Further study shows that it is the contribution from large orbital anglular momenta, which the Langevin cross section overestimates. Orbiting complexes (of H⁺ around D₂) play a negligible role, and are very short-lived. The lifetime of strongly coupled complexes is estimated to be 450 E^?1.3 fs, where E is the total energy in eV. The use of trajectory data to improve Light's phase space theory is discussed.     

Experimental and theoretical studies of the reaction Ba+(D2, D)BaD+: sequential impulse model for endothermic reactions

The sequential impulse model for direct reactions of Mahan, Ruska and Winn is extended to include endothermic reactions. The model is outlined and used to predict the variation in cross section with kinetic energy for heavy atom—light homonuclear diatom reactions. The results are found to agrees well with experimental data for the reaction Ba⁺(D₂, D)BaD⁺. The bond dissociation energy of BaD⁺, 2.5 ± 0.1 eV, and the proton affinity of Ba, 250 ± 3 kcal/mol, are derived.     

Experimental determination of repulsive potentials between alkali ions (Li+, Na+, and K+) and N2 and CO molecules

Integral scattering cross sections have been measured for alkali ions (Li⁺, Na⁺ and K⁺) in the energy range 500–4000 eV scattered by room temperature N₂ and CO molecules through effective laboratory angles greater than 5 × 10^?3 rad. The repulsive potentials deduced from the cross sections are represented bya practically identical formula for the Na⁺N₂ and Na⁺CO systems, and for the K⁺CO systems, respectively, while the repulsive potentials of the Li⁺N₂ system are somewhat smaller than those of the Li⁺CO system at larger intermolecular distances.     

New cross section functions for hot 18F atom collisions with H2, HD and D2

New analytic reaction cross-section functions are reported for hot ¹⁸F atoms reacting with H₂, HD and D₂. A realistic model is proposed for the total non-reactive cross section in these systems throughout the center-of-mass collision energy range 0–100 eV.     

Kinetics of HD exchange in the reaction of HBF2 with D2

The rate constant for the unusually rapid HD exchange reaction of D₂ with HBF₂ : D₂(g) + HBF₂(g) → DBF₂(g) + HD(g) has been measured (k₂(298K) = (7.42 ± 2.0) × 10^?23 cm³/molecule s). The activation energy for this reaction has been estimated to be 17.8 ± 1.2 kcal/mole. The mechanism probably involves a multicenter orbital interaction between D₂ and HBF₂.     

Photoionization study of Hg2

Photoionization efficiency data for Hg₂⁺ have been obtained in the region of 650–1400 A. The ionization energy of Hg₂ was determined to be 9.103 ± 0.010 eV. This value allows the calculation of the dissociation energy of Hg⁺₂ to be 1.40 ± 0.02 eV. By analyzing the differences in energy between corresponding autoionization peaks observed in the Hg⁺ and the Hg₂⁺ spectra and by assuming the charge induced-dipole interaction to be the dominant interaction between Hg⁺(²D_{5/2, 3/2}) and Hg at the equilibrium bond distance of Hg₂, the equilibrium bond distance for Hg₂ was deduced to 3.35 A.     

The platinumcarbon bond strength in Pt(PPh3)2(CH3)I

The enthalpies of reaction 1–3 have been determined

as ΔH(1) = ?176.6 ± 5.4, ΔH(2) = ?107.8 ± 6.0, and ΔH(3) = ?78.9 ± 2.0 kJ mol^?1. The bond dissociation energy difference D₁(PtCH₃) ? D₁(PtI) = +6 ± 5 kJ mol^?1 is calculated, which indicates that the two bonds have very similar strengths.     

The enthalpies of formation of CH3Mn(CO)5 and of CH3Re(CO)5, and the strengths of the CH3Mn and CH3Re bonds

From measurements of the heats of iodination of CH₃Mn(CO)₅ and CH₃Re(CO)₅ at elevated temperatures using the ‘drop’ microcalorimeter method, values were determined for the standard enthalpies of formation at 25° of the crystalline compounds: ΔH^o_f[CH₃Mn(CO)₅, c] = ?189.0 ± 2 kcal mol^?1 (?790.8 ± 8 kJ mol^?1), ΔH^o_f[Ch₃Re(CO)₅,c] = ?198.0 ± kcal mol^?1 (?828.4 ± 8 kJ mo^?1). In conjunction with available enthalpies of sublimation, and with literature values for the dissociation energies of MnMn and ReRe bonds in Mn₂(CO)₁₀ and Re₂(CO)₁₀, values are derived for the dissociation energies: D(CH₃Mn(CO)₅) = 27.9 ± 2.3 or 30.9 ± 2.3 kcal mol^?1 and D(CH₃Re(CO)₅) = 53.2 ± 2.5 kcal mol^?1. In general, irrespective of the value accepted for D(MM) in M₂(CO)₁₀, the present results require that, D(CH₃Mn) = $\text{1}\text{2}$D(MnMn) + 18.5 kcal mol^?1 and D(CH₃Re) = $\text{1}\text{2}$D(ReRe) + 30.8 kcal mol^?1.     

Electron scattering differential cross sections for C2H2, C2H4, and C2H6 by gas phase electron diffraction - binding effects

Experimental differential cross sections for 40 keV electrons scattered by C₂H₂, C₂H₄ and C₂H₆ molecules were measured using the gas electron diffraction method in the range of the scattering variable s from s = 1 A^?1 to s = 30 A^?1. The differential cross sections for neon were also measured and compared with calculated differential cross sections to calibrate the diffractograph. Experimental differential cross sections show significant deviations with respect to theoretical differential cross sections calculated from the Debye-Ehrenfest model, mainly in the range of small scattering angles. The observed differences are connected to chemical binding effects. From the experimental data, an estimation of the binding energy was carried out. The deduced values: ?0.58 ± 0.20 au for C₂H₂, ?0.94 ± 0.30 au for C₂H₄ and ?1.23 ± 0.40 au for C₂H₆ are in agreement with those obtained by thermochemical methods.     

Beam-gas chemiluminescent reactions of Eu and Sm with O3, N2O,NO2 and F2

Studies are made of the visible chemiluminescence resulting from the reaction of an atomic beam of samarium or europium with O₃, N₂O, NO₂ and F₂ under single-collision conditions (～10^?4 torr). The spectra obtained for SmO, EuO, SmF, and EuF are considerably more extensive than previously observed. The variation of the chemiluminescent intensity with metal flux and with oxidant flux is investigated, and it's concluded that the reactions are bimolecular. From the short wavelength curoff of the chemiluminescent spectra, the following lower bounds to the ground state dissociation energies are obtained: D⁰₀(SmO) > 135.5 +- 0.7 kcal/mole, D⁰₀(EuO) > 131.4 ± 0.7 kcal/mole, D⁰₀(SmF) > 123.6 ± 2.1 kcal/mole, and D⁰₀(EuF) > 129.6 ± 2.1 kcal/mole. Using the Clausius-Clapeyron equation, the latent heats of sublimation are found to be ΔH₁₀₅₂ (Eu) = 42.3 ± 0.7 kcal/mole for europium and ΔH₁₀₈₄(Sm) = 47.9 ± 0.7 kcal/mole for samarium. Total phenomena- logical cross sections are determined for metal atom removal. Relative photon yields per product molecule are calculated from the integrated chemiluminescent spectra and it is found that Sm + F₂ → SmF^* + F is the brightest reaction. The comparison of the photon yields under single-collision conditions with those at several torr shows that energy transfer collisons play an important role in the mechanism for chemiluminescence at the higher pressures. A simple model is presented which explains the larger photon yields of the Sm reactions compared to the Eu reactions in terms of the greater number of electronic states correlating with the reactants in the case of samarium.     

Formation of WF−6 and its dissociative products by collisional ionization

The formation of negative ions in electron transfer reactions between hyperthermal alkali atoms (Na, K) and WF₆ has been studied in the energy range 0–30 eV c.m. Relative cross sections and translational energy thresholds for ion pair formation have been measured, from which the following electron affinities (EA) and bond dissociation energies (D) have been derived: EA(WF₆) = 3.7 eV, EA(WF₅) = 1.25 eV, D(WF₅—F) = 5.1 eV, D)WF₅—F^?) = 5.4 eV, D(WF^?₅—F) = 7.6 eV. Several ion molecule reactions are discussed which result in formation of secondary fragmentation ions and WF^?₇.     

Predissociation of the c3Πu state of H2, populated after charge exchange of H2+ with several targets at keV energies

A detailed study of the predissocitation of the c³Π_u state of H₂ has been made with a new, very sensitive, experimental technique. A resolution better than 1% is obtained in the measurement of the released kinetic energy of HH pairs after charge exchange of H₂⁺ with Ar, H₂, Mg, Na and Cs by detecting both fragments with a time- and position-sensitive microchannel-plate detector. Eighteen vibrational levels of the c³Π_u state can be clearly distinguished in the range of 7.2–10.2 eV. Detailed information is extracted from the spectra with the aid of a convolution procedure. The vibrational energy levels of the c³Π_u state as calculated by Ko?os and Rychlewski are found to be correct within the experimental accuracy of 5 meV. Predissociative lifetimes are measured, yielding 6.2±0.5 ns for the lowest rovibrational level (υ = 0, N = 1), which are in good agreement with theoretical calculations of Comtet and de Bruijn. The cross section for charge exchange is observed to increase gradually with the vibrational level and seems to follow the geometrical cross section of the molecule. Rotational excitation during the charge exchange is also found to increase considerably with the vibrational quantum number. The final rotational temperature further depends strongly on the target gas used and increases with the resonance energy defect ΔI in the charge exchange collision.     

Close-coupling elastic and inelastic integral and differential cross sections for Li+ + H2 collisions

The quantum mechanical close-coupling formalism is applied to the study of elastic and rotationally inelastic Li⁺ + H₂ collisions making use of the Kutzelnigg-Staemmler-Hoheisel potential energy surface. Integral and differential cross sections for j = 0 → 0 and j = 0 → 2 are obtained in the collision energy range 0.2 to 0.9 eV and for j = 1 → 1 and j = 1 → 3 at 0.6 eV. A rainbow structure is observed in both the elastic and inelastic angular distributions and a quenching of the fast oscillations is found in the cross sections for j = 1 initially compared to the case j = 0 initially. At 0.6 eV. the calculated quantum mechanical angular distributions are compared to those from a classical trajectory calculation using the same surface and to the experimental ones. The dynamics of rotational excitation in the Li⁺ + H₂ system is contrasted to rotational excitation in systems for which the atom-diatom interaction is predominantly repulsive.     

A State-selected study of the symmetric charge transfer reaction H2+ + H2

We have measured the relative total charge transfer cross sections of H₂⁺ + H₂ as a function of the vibrational state of H₂⁺, υ′_o = 0–4. using the crossed ion-neutral beam and high-resolution photoionization methods. The experimental results obtained at a center-of-mass collisional energy of 22.5 eV are found to be in excellent agreement with a recent theoretical study.     

The effect of internal excitation on the collision induced dissociation of I+2(2Πg,υ) ions

Cross sections for collision induced dissociation of 0.65 to 3.2 keV I⁺₂(²Π_g, υ) ions in I⁺₂(²Π_g, υ) + N₂(X ¹Σ⁺_g, υ = 0) interactions have been determined. Reaction cross sections for I⁺₂(²Π_{$\text{3}\text{2}$,g}, υ) ions in low vibrational levels vary smoothly from 6 to 10 A² with increasing kinetic energy. Dissociation cross sections for I⁺₂(²Π_{$\text{1}\text{2}$,g}, υ) ions are larger than those involving ground state ions. Processes involving highly excited metastable states of I⁺₂ are not observed in this investigation.     

Measurements of differential cross sections for vibrational quantum transitions in scattering of Li+ on H2

A pulsed monoenergetic ⁷Li⁺ ion beam (lab. energy 10–40 eV) is scattered from a highly collimated (= 1.5°) H₂ nozzle beam. The time-of-flight spectrum of the ions scattered in the forward laboratory direction shows both a fast peak corresponding to forward center-of-mass scattering and a slow peak corresponding to wide-angle center-of-mass scattering. These peaks have been further resolved to show contributions from individual vibrational quantum transitions. From an analysis of the time-of flight spectra the differential inelastic cross sections for a wide range of angles and energies between 2 eV <E_cm < 9 eV have been determined. The spectra also contain information on rotational inelastic cross sections.     

Laser induced photodissociation of H+2 and D+2 ions

Photodissociation of H⁺₂ and D⁺₂ has been observed in a crossed beam experiment. A laser used as photon source. The ion and laser beam cross each other inside the laser cavity. The momentum spectra of the resulting H⁺ or D⁺ fragments are recorded with a mass spectrometer. From the spectra the excess kinetic energy is calculated. These values agree with the theoretically expected ones within the experimental error. From the measured intensity distribution the relative population for several vibrational states in the primary ion beam is calculated. Our values deviate from the usual assumed Franck-Condon pattern as well as from the values reported by Dunn. The angular dependence of the fragments is also measured. This dependence indicates a polarization of the primary beam perpendicular to its direction.     

Time-dependent close coupling for vibrational excitation in three dimensions: Application to H+ - H2

Impact parameter calculations for the non-reactive H⁺ + H₂ (n_i = 0) → H⁺ + H₂ (n_f) collision are reported for energies 10 eV ? E_cm ? 200 eV describing the rotational motion of the molecule in the sudden limit. The time-dependent Schrödinger equation for the vibrational motion has been solved by close coupling techniques expanding the vibrational wavefunction into both harmonic and numerically exact H₂ bound states. The convergence in vibrational basis sets, where up to six vibrational levels are considered, becomes worse with decreasing energy and increasing inelasticity. Furthermore, the harmonic wavefunctions are not suitable over a large range of energies to calculate proper cross sections. The various integral and differential cross sections have been compared with the classical results of Giese and Gentry.     

Dynamics of the reaction H2+(He,H)HeH+. Influence of various forms of reactant energy on the total and differential cross section

Results of quasiclassical trajectory calculations of reactive processes between He atoms and H₂⁺ (υ, J) molecular ions in the collision energy interval 0.5–5.0 eV (c.m.) for a large number of selected υ, J combinations are analyzed with respect to the influence of the initial translational, vibrational, and rotational energy on the total and differential reaction cross sections. Vibrational energy is more effective in promoting the reaction than translational energy. Small rotational excitation has a negligible effect, whereas high rotational excitation has a similar influence on the reaction cross sections as the vibrational excitation of the same magnitude.