Rotational excitations in para-H2+para-H2 collisions: full- and reduced-dimensional quantum wave packet studies comparing different potential energy surfaces

We study the process of rotational excitation in the collisions of para-H(2) with para-H(2) by propagating wave packets with the multiconfiguration time-dependent Hartree (MCTDH) algorithm. Transition probabilities are then calculated by the method of Tannor and Weeks based on time-correlation functions. Calculations were carried out up to a total angular momentum of J=70 to compute integral cross sections up to 1.2 eV in collision energy and thermal rate coefficients from 100 to 3000 K. The process is studied on the full-dimensional potential energy surface of Boothroyd-Martin-Keogh-Peterson (BMKP) as well as on the rigid rotor surface of Diep and Johnson. We test the validity of the rigid rotor approximation by also considering two rigid rotor restrictions of the BMKP potential energy surface (PES). Additionally, we investigate a variant of the BMKP PES suggested by Pogrebnya and Clary [Chem. Phys. Lett. 363, 523 (2002)] with reduced anisotropy. We compare our results with previous theoretical data for the cross sections and with experimental data for the rate coefficients at low temperatures.     

Calculations of fine-structure resolved collisional rate coefficients for the NH(X3Σ-)-He system

We present fine-structure-resolved collisional rate coefficients for the NH(X(3)Σ(-))-He van der Waals complex. The calculations are based on the state-of-the-art potential energy surface [Cybulski et al., J. Chem. Phys. 122, 094307 (2005)]. Close-coupling calculations of the collisional excitation cross sections of the fine-structure levels of NH by He are calculated for total energies up to 3500 cm(-1), which yield, after thermal average, rate coefficients up to 350 K. The fine-structure splitting of rotational levels is taken into account rigorously. The propensity rules between fine-structure levels are reported, and it is found that F-conserving cross sections are much larger than F-changing cross sections, as expected from theoretical considerations. The calculated rate coefficients are compared with available experimental measurements at room temperature and a fairly good agreement is found between experimental and theoretical data. The agreement confirms the relatively good quality of the scattering calculations and also the accuracy of the potential energy surface used in this work. The new set of thermal rate coefficients for this system may be used for improvements in astrophysical and atmospherical modeling.     

Dissociative Excitation of Lead Atom 6pnd Levels in Electron Collisions with Lead Dichloride Molecules

Dissociation excitation of the 6pnd levels of the lead atom in e–PbCl₂ collisions resulting in the population of metastable PbI levels via cascade transitions was experimentally studied. Cross sections for the cascade population of the 6p2 levels at an incident electron energy of 100 eV were determined. The dissociative excitation cross sections measured were compared with the excitation cross sections in e–Pb collisions.     

Close-coupling study of rotational energy transfer and differential scattering in H2O collisions with He atoms

Quantum close-coupling scattering calculations of rotational energy transfer (RET) of rotationally excited H(2)O due to collisions with He are presented for collision energies between 10(-6) and 1000 cm(-1) with para-H(2)O initially in levels 1(1,1), 2(0,2), 2(1,1), and 2(2,0) and ortho-H(2)O in levels 1(1,0), 2(1,2), and 2(2,1). Quenching cross sections and rate coefficients for state-to-state RET were computed. Both elastic and inelastic differential cross sections are also calculated and compared with relative experimental results giving generally good agreement in all cases, but less so for inelastic results. Significant differences in the computed collisional parameters, obtained on three different potential energy surfaces (PESs), were found particularly in the ultracold regime. In the thermal regime, the rate coefficients calculated on each of the surfaces are generally in better agreement and comparable, but typically larger, than those obtained in a previous calculation. Unfortunately, a lack of absolute differential or integral inelastic experimental data prevents firm determination of a preferred PES.     

Vibrationally resolved rate coefficients and branching fractions in the dissociative recombination of O2+

We have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.4 eV for five different vibrational populations of the ion beam, as well as the partial (vibrationally resolved) rate coefficients and the branching fractions near 0 eV collision energy for the vibrational levels v=0, 1, and 2. The vibrational populations used were produced in a modified electron impact ion source, which has been calibrated using Cs-O(2)(+) dissociative charge transfer reactions. The measurements indicate that at low collision energies, the total rate coefficient is weakly dependent on the vibrational excitation. The calculated thermal rate coefficient at 300 K decreases upon vibrational excitation. The partial rate coefficients as well as the partial branching fractions are found to be strongly dependent on the vibrational level. The partial rate coefficient is the fastest for v=0 and goes down by a factor of two or more for v=1 and 2. The O((1)S) quantum yield, linked to the green airglow, increases strongly upon increasing vibrational level. The effects of the dissociative recombination reactions and super elastic collisions on the vibrational populations are discussed.     

State-to-state rotational transitions in H2+H2 collisions at low temperatures

We present quantum mechanical close-coupling calculations of collisions between two hydrogen molecules over a wide range of energies, extending from the ultracold limit to the superthermal region. The two most recently published potential energy surfaces for the H(2)-H(2) complex, the so-called Diep-Johnson (DJ) [J. Chem. Phys. 112, 4465 (2000); 113, 3480 (2000)] and Boothroyd-Martin-Keogh-Peterson (BMKP) [J. Chem. Phys. 116, 666 (2002)] surfaces, are quantitatively evaluated and compared through the investigation of rotational transitions in H(2)+H(2) collisions within rigid rotor approximation. The BMKP surface is expected to be an improvement, approaching chemical accuracy, over all conformations of the potential energy surface compared to previous calculations of H(2)-H(2) interaction. We found significant differences in rotational excitation/deexcitation cross sections computed on the two surfaces in collisions between two para-H(2) molecules. The discrepancy persists over a large range of energies from the ultracold regime to thermal energies and occurs for several low-lying initial rotational levels. Good agreement is found with experiment B. Mate et al., [J. Chem. Phys. 122, 064313 (2005)] for the lowest rotational excitation process, but only with the use of the DJ potential. Rate coefficients computed with the BMKP potential are an order of magnitude smaller.     

Resonant vibrational excitation and de-excitation of N2(v) by low-energy electrons

We have calculated cross sections and rate coefficients for low-energy electron impact excitation of the nitrogen molecule from vibrationally excited levels N2(v) 1-8. Calculations are performed in the 2Pig shape resonance energy region, from 0 to 5 eV. The cross sections are determined by using our recent integral cross section measurements of the ground level vibrational excitation and the most recent cross sections for elastic electron scattering, applying the principle of detailed balance. The rate coefficient calculations are performed for the Maxwellian electron energy distribution. By using extended Monte Carlo simulations, the electron energy distribution functions (EEDF) and the rate coefficients are also determined for the nonequilibrium conditions, in the presence of the homogeneous external electric field for the typical, moderate values of the electric field over gas number density ratios, E/N.     

Quenching of rotationally excited CO by collisions with H2

Quantum close-coupling and coupled-states approximation scattering calculations of rotational energy transfer in CO due to collisions with H2 are presented for collision energies between 10(-6) and 15,000 cm(-1) using the H2-CO interaction potentials of Jankowski and Szalewicz [J. Chem. Phys. 123, 104301 (2005); 108, 3554 (1998)]. State-to-state cross sections and rate coefficients are reported for the quenching of CO initially in rotational levels j2 = 1-3 by collisions with both para- and ortho-H2. Comparison with the available theoretical and experimental results shows good agreement, but some discrepancies with previous calculations using the earlier potential remain. Interestingly, elastic and inelastic cross sections for the quenching of CO (j2 = 1) by para-H2 reveal significant differences at low collision energies. The differences in the well depths of the van der Waals interactions of the two potential surfaces lead to different resonance structures in the cross sections. In particular, the presence of a near-zero-energy resonance for the earlier potential which has a deeper van der Waals well yields elastic and inelastic cross sections that are about a factor of 5 larger than that for the newer potential at collision energies lower than 10(-3) cm(-1).     

Bimolecular reactions of vibrationally excited molecules. Roaming atom mechanism at low kinetic energies

Quasiclassical trajectory calculations have been performed for the H + H'X(v) → X + HH' abstraction and H + H'X(v) → XH + H' (X = Cl, F) exchange reactions of the vibrationally excited diatomic reactant at a wide collision energy range extending to ultracold temperatures. Vibrational excitation of the reactant increases the abstraction cross sections significantly. If the vibrational excitation is larger than the height of the potential barrier for reaction, the reactive cross sections diverge at very low collision energies, similarly to capture reactions. The divergence is quenched by rotational excitation but returns if the reactant rotates fast. The thermal rate coefficients for vibrationally excited reactants are very large, approach or exceed the gas kinetic limit because of the capture-type divergence at low collision energies. The Arrhenius activation energies assume small negative values at and below room temperature, if the vibrational quantum number is larger than 1 for HCl and larger than 3 for HF. The exchange reaction also exhibits capture-type divergence, but the rate coefficients are larger. Comparisons are presented between classical and quantum mechanical results at low collision energies. At low collision energies the importance of the exchange reaction is enhanced by a roaming atom mechanism, namely, collisions leading to H atom exchange but bypassing the exchange barrier. Such collisions probably have a large role under ultracold conditions. The calculations indicate that for roaming to occur, long-range attractive interaction and small relative kinetic energy in the chemical reaction at the first encounter are necessary, which ensures that the partners can not leave the attractive well. Large orbital angular momentum of the primary products (equivalent to large rotational excitation in a unimolecular reaction) is favorable for roaming.     

Dissociative Excitation of Nickel Quintet States upon Electron Collisions with NiCl2Molecules

Dissociative excitation of nickel atom quintet states upon electron collisions with nickel dichloride molecules was studied by means of the extended crossed beams technique combined with optical spectroscopy. Forty excitation cross sections were measured at an electron energy of 100 eV. Two optical excitation functions were detected in the electron energy range 0–100 eV. Possible reaction channels at low electron energies were analyzed. Cross sections for dissociative excitation were compared to those for direct excitation upon electron collisions with nickel atoms.     

Dissociative excitation of the singly charged lead ion in electron collisions with PbCl2 molecules

Inelastic collisions of slow electrons with lead dichloride molecules yielding excited lead ions in a single encounter event were studied by the extended crossed-beam technique. At an incident electron energy of 100 eV, 67 cross sections for dissociative excitation of PbII spectral lines were measured. Three optical excitation functions were determined in the electron energy range 0–100 eV. The obtained results are compared with data on excitation cross sections of PbII in electron-atom collisions.     

Coupled-states statistical investigation of vibrational and rotational relaxation of OH(2pi) by collisions with atomic hydrogen

We report state-to-state cross sections and thermal rate constants for vibrational and rotational relaxation of OH(2pi) by collision with H atoms. The cross sections are calculated by the coupled-states (CS) statistical method including the full open-shell character of the OH + H system. Four potential energy surfaces (PESs) ((1,3)A' and (1,3)A') describe the interaction of OH(X2pi) with H atoms. Of these, three are repulsive, and one (1A') correlates with the deep H2O well. Consequently, rotationally and ro-vibrationally inelastic scattering of OH in collisions with H can occur by scattering on the repulsive PESs, in a manner similar to the inelastic scattering of OH by noble gas atoms, or by collisions which enter the H2O well and then reemerge. At 300 K, we predict large (approximately 1 x 10(-10) cm3 molecule(-1) s(-1)) vibrational relaxation rates out of both v = 2 and v = 1, comparable to earlier experimental observations. This anomalously fast relaxation results from capture into the H2O complex. There exists a significant propensity toward formation of OH in the pi(A') lambda-doublet level. We also report state-resolved cross sections and rate constants for rotational excitation within the OH v = 0 manifold. Collisional excitation from the F1 to the F2 spin-orbit manifold leads to an inverted lambda-doublet population.     

Dissociative Excitation of Even Doublet Levels of the Cobalt Atom in Electron Collisions with Cobalt Dichloride Molecules

The dissociative excitation of the even doublet levels of the cobalt atom upon the collisions of cobalt dichloride molecules with 100-eV monoenergetic electrons was experimentally studied. Dissociative excitation cross sections for transitions from these levels turned out to be greater than the corresponding cross sections of direct excitation in electron-atom collisions (except for the e ² P _1/2 level). The total excitation cross sections (including the contribution of cascade population) were determined for ten levels.     

Formation of excited tin ion in collisions of slow electrons with SnCl2 molecules

Formation of excited tin ions in collisions of slow electrons with tin dichloride molecules was studied experimentally. Fifty excitation cross sections for SnII at an electron energy 100 eV were measured. Six optical functions for dissociative excitation were detected in the electron energy range 0–100 eV. Cross sections for direct and dissociative excitation of several lines were compared. Dissociative excitation in the spectral bands of two transitions in SnCl was also studied.     

Ion-pair formation in fast collisions of metastable argon with iodine

Differential ion-pair production cross sections for Ar^*—I₂ collisions at center of mass energies of 25–133 eV are quite similar to analogous alkali—I₂ results despite the addition of competing channels (Penning ionization and excitation transfer) and possible multiple electronic surface crossings.     

Accurate quantum wave packet calculations for the F + HCl → Cl + HF reaction on the ground 1(2)A' potential energy surface

We present converged exact quantum wave packet calculations of reaction probabilities, integral cross sections, and thermal rate coefficients for the title reaction. Calculations have been carried out on the ground 1(2)A' global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys. 124, 224303 (2006)]. Converged wave packet reaction probabilities at selected values of the total angular momentum up to a partial wave of J = 140 with the HCl reagent initially selected in the v = 0, j = 0-16 rovibrational states have been obtained for the collision energy range from threshold up to 0.8 eV. The present calculations confirm an important enhancement of reactivity with rotational excitation of the HCl molecule. First, accurate integral cross sections and rate constants have been calculated and compared with the available experimental data.