Collision induced fragmentation of mass-selected (CO2) n + clusters

The collisional velocity dependence of the cross sections for fragmentation of mass-selected (CO₂) _n ⁺ (n+2...7) clusters in collisions with Ar atoms is presented. Interesting structure can be observed in the cross sections which indicate that the collision occurs between the Ar atom and one CO₂ molecule within the cluster. The results may be explained by assuming that the collision leads to either vibrational excitation of a loosely bound CO₂ monomer which then leaves the cluster or excitation of the entire cluster to a dissociative state.     

Semiclassical calculation of energy transfer in polyatomic molecules. IX. Cross sections for M + CO2 (000) → M + CO2(nml) (M = He and Ar)

Cross sections for excitation of the asymmetric-stretch vibrational manifold of CO₂ in collision with He and Ar have been calculated using a semiclassical collision method and a potential-energy surface constructed from self-consistent field data. The cross sections for collisional energies up to 2.0 eV are compared with those obtained in a molecular-beam experiment.     

Distorted wave calculations of the vibrational relaxation of CO in collision with He atoms

Cross sections are calculated for vibrational relaxation of the CO/He system. The calculations use the exponential distorted wave, the distorted wave and close-coupling techniques for the vibrational motion. Rotational motion is treated with the infinite-order sudden approximation. Good agreement is shown between the distorted wave methods and the close-coupled calculations. Vibrational relaxation rate constants are calculated and compared with experimentally determined values. The distorted wave approximation is shown to provide results of useful accuracy.     

Vibrational excitation of SF6 in collisions with He atoms

Vibrational excitation of SF₆ molecules in collisions with He atoms is studied using a vibrational close-coupling, rotational infinite-order-sudden method of calculation. Integral and differential cross sections for excitation of the triply degenerate ν₆ and ν₅ vibrational modes of SF₆ are reported for thermal collisional energies. Excitation of the ν₆ mode is found to be particularly efficieny. The cross sections are much larger than those calculated previously for the excitation of the bending mode in the He + CO₂ system. The differential cross sections are backward peaked.     

Semiclassical calculation of energy transfer in polyatomic molecules. V. Differential cross sections for excitation of CO2 and N2O colliding with Li+ at E ≈ 4.72 eV

A semiclassical model has been used to calculate differential cross sections for vibrational excitation of CO₂ and N₂O at the center of mass collision energy E≈ 4.72 eV. Also the average rotational excitation as a function of the scattering angle is reported. Comparison is made with experimental data and previous more approximate theoretical calculations.     

Basis-set effects in quantum-mechanical calculations of translational-to-vibrational energy transfer in O(3P) + CO2 collisions

Cross sections for the vibrational excitation of CO₂ in collisions with O(³P) from the ground state to the (00⁰1) state are computed using vibrational-close-coupling with the infinite-order-sudden approximation for rotation (VCC IOS). For a relative translational energy of 3 eV, several vibrational basis sets are tested for convergence of this cross section. Using the best converged vibrational basis set for 3 eV, the (00⁰1) → (00⁰1) cross section is computed over the relative translational energy range of 2 to 6 eV. Previous discrepancies of factors of 2 to 7 between the VCC IOS method and quasiclassical trajectory studies are reduced to factors of 1.1 to 2.5.     

A model study of vibrational excitation of carbon dioxide molecule by slow electrons: the role of wave packet sliding from the ridge

The method of an accurate calculation of vibrational excitation cross sections of a two-mode molecule by slow electrons within the framework of the local theory (the ‘boomerang’ model) is applied for a model study of the excitation of the symmetrical stretching vibrational modes of carbon dioxide in the two-mode approximation (i.e., only the symmetrical stretch and bending modes are included in the consideration). It is shown that the 'boomerang’ oscillations in the cross section are strongly suppressed due to the decay of the one-dimensional ‘boomerang' state caused by the anion wave packet sliding from the linear configuration ridge. Consequently, the bending motion in CO₂ molecule should to be taken into account even if only the processes without the final bending excitation are considered. A simple quasi one-dimensional model describing the system sliding from the ridge is put forward which treats this phenomenon as a decay of the initial wave packet via the series of diabatic resonant states related to unstable trajectory.     

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.     

Observation of the fourth positive system of CO in dissociative recombination of vibrationally excited CO+2

The CO fourth positive system obtained by dissociative recombination of CO₂⁺(X̃²π_g) ions has been observed under various conditions of CO₂⁺ vibrational excitation. It is shown that the CO(A¹π) vibrational distribution is directly linked to CO⁺₂ excitation. Implications for planetary airglows are discussed.     

Neutral scattering and vibrational excitation in K+Br2 Collisions

Differential cross sections are presented for neutral scattering of K atoms in collisions with Br₂ molecules in the energy range from 20 to 150 eV. In addition energy-loss spectra for the scattered K atoms are shown. The differential cross sections show a large peak near the forward direction. The energy-loss spectra point to considerable vibrational excitation at small angles. The results are attributed to reneutralization from an ion-pair state formed during the collision. In some cases this process can involve three potential surface crossings. The experimental results can be reproduced in simple trajectory calculations on diabatic potential surfaces. The calculations show that the forward scattering is rainbow scattering, caused by the internal motion of the Br₂^? molecular ion during the collision. There is no analog to this rainbow in atom-atom scattering. The internal moti is also responsible for the observed vibrational excitation.     

The centrifugally decoupled exponential distorted wave (CDEDW) approximation for the calculation of rotationally inelastic molecular collision cross se

A new approximate method is presented for the rapid calculation of rotationally inelastic molecular collision cross sections. The method is called the centrifugally decoupled exponential distorted wave (CDEDW) approximation and involves the combination of two well known approximations. The first approximation is the neglect of the off-diagonal coupling terms which arise from the orbital angular momentum operator in the coupled differential equations in the body-fixed axis system. The second approximation is to treat the remaining coupling terms, which arise from the interaction potential, using a unitary perturbation approximation. The CDEDW method is applied to the calculation of total and partial rotationally inelastic cross sections in the ArN₂ system, and detailed comparisons are made with exact and several other types of approximate calculations. Agreement with exact calculations is good and often comparable with the coupled states and p-helicity decoupled approximations. The CDEDW method requires a similar amount of computational effort to the infinite order sudden (IOS) approximation, and we show that for the present system the CDEDW method gives more reliable results.     

Fully converged sudden rotation total integral cross sections for 4He + H2 (ν = 0, j = 0) → 4He + H2 (ν′ = 1, j′)

Total integral cross sections for ⁴He + H₂ (ν = 0, j = 0) → ⁴He + H₂ (ν′ = 1, j′ = 0, 2) have been calculated in the total energy range 1.2 to 5.5 eV, according to a quantal sudden approximation for the H₂ rotational degrees of freedom and a close coupling expansion of the vibrational degree of freedom. Convergence of the above cross sections is investigated by employing four vibration basis sets in the close coupling calculations, i.e., ν = 0,1, ν = 0,1, 2, ν = 0, 1, 2, 3 and ν = 0, 1, 2, 3, 4. Between 4.2 and 5.5 eV calculations were done with three vibration basis sets; ν = 0.–4, ν = 0–5, and ν = 0–6. It is found that at least four vibrational basis functions are needed to converge (to within 5–10%) these cross sections in the above energy range. Comparison of breathing sphere calculations and summed sudden rotation results shows good agreement for the (weakly anisotropic) Mies-Krauss potential. However, as expected the former results underestimate the vibrational 0 → 1 total integral cross sections.     

Vibrational matrix elements of the quadrupole moment functions of H2, N2 and CO

The quadrupole moment functions (molecular quadrupole moment versus internuclear distance) have been determined by quantum mechanical calculations for H₂ (by Kolos and Wolniewicz), N₂ (by Wahl and Nesbet), and CO (by Nesbet). These functions are used with numerical vibrational wave functions to compute matrix elements which are useful for calculations of scattering cross sections, energy transfer rates and excitation probabilities, and infrared intensities of forbidden bands.     

Collision-induced intramolecular vibration—vibration energy transfer in CO2: CO2(0001) + H2/D2

Intramolecular vibration—vibration energy transfer cross sections have been calculated for CO₂(00⁰1) + H₂/D₂ → CO₂(11¹0) + H₂/D₂, → CO₂(10⁰0) + H₂/D₂, and → CO₂(20⁰0) + H₂/D₂ based on the mechanism that the energy mismatch is transferred to the translational motion. For CO₂ + H₂, the calculated cross section for CO₂(00⁰1) + H₂ → CO₂(10⁰0) + H₂ is in good agreement with experimental data. Cross sections for the processes (00⁰1 → 11¹O) and (00⁰1 → 20⁰0) are found to be too small compared with experimental data. For CO₂ + D₂, (00⁰1 → 10⁰0) is also the most important process and appears to represent experimental data at room temperature. The sum of three cross sections of CO₂ + H₂ is always greater than that of CO₂ + D₂ over the temperature range of 100–2500 K.     

Excitation of He—41 D-substates by He+- and Ne+-projectiles investigated by level-crossing techniques

Collisions of He⁺- and Ne⁺-projectiles with He at impact energies between 90 keV and 800 keV were investigated. Relative excitation cross sections for magnetic sublevels of He—4¹ D were determined using level-crossing techniques. Absolute excitation cross sections σ _m of the Zeeman-sublevels are given using He—4¹ D cross sections from earlier measurements. The results show strong variations of the cross sections σ₀ and σ_±1 with a quasi-oscillatory behaviour. σ_±2 is much smaller than σ₀ and σ_±1.     

Validity of the rotational sudden approximation for vibrational relaxation in He + CO

Calculations of cross sections and rate constants are reported for the vibrational relaxation of CO in collision with ³He and ⁴He. Results computed using a semiclassical technique and a vibrational close-coupling, rotational infinite-order sudden method are compared.     

Calculation of differential cross sections for rotational excitation in D2 + CO collisions at 87.2 meV

Differential cross sections for rotational excitation in D₂ + CO collisions are calculated at six scattering angles using an electron gas surface and a semiclassical scattering theory in which the translational and the rotational motion of CO are treated classically whereas the D₂ rotation is quantized.     

Experimental and theoretical determination of rate constants for vibrational relaxation of CO2 and CH3F by He

Rate constants have been measured for the vibrational relaxation of CO₂ and CH₃F in the temperature range 300-150 K by the collision partners ⁴He and ³He. These results are compared with those calculated with a vibrational close-coupling, rotational infinite-order sudden approximation.     

The quantum dynamics of the reactions N+H2(HD,D2) and their vibrational excitation effect

The N(⁴S)+H₂ reaction and its isotopic variants have been investigated by means of time‐dependent quantum wave packet with split operator method on the ground state potential energy surface (Zhai and Han, J. Chem. Phys. 2011, 135, 104314). The reaction probabilities, integral cross sections, branching ratio of the integral cross sections, and effect of vibrational excitation of H₂, HD, and D₂ diatomic molecules are presented and discussed. The results reveal that the intramolecular isotopic effect is greater than the intermolecular one, and that the vibrational excitation of the diatomic molecules can promote the progress of this reaction. In addition, a limited number of rigorous Coriolis coupling calculations of the integral cross sections of the N(⁴S)+H₂ reaction have been carried out. Also shown is that since the Coriolis coupling plays a small part in this accurate quantum calculation, the cheaper centrifugal sudden calculations here reported are effective for this reactive system. © 2014 Wiley Periodicals, Inc.