Vibrational inelastic and charge transfer processes in H(+)+H2 system: an ab initio study

State-resolved differential cross sections, total and integral cross sections, average vibrational energy transfer, and the relative probabilities are computed for the H(+)+H2 system using the newly obtained ab initio potential energy surfaces at the full CI/cc-pVQZ level of accuracy which allow for both the direct vibrational inelastic and the charge transfer processes. The quantum dynamics is treated within the vibrational close-coupling infinite-order-sudden approximation approach using the two ab initio quasidiabatic potential energy surfaces. The computed collision attributes for both the processes are compared with the available state-to-state scattering experiments at E(c.m.)=20 eV. The results are in overall good agreement with most of the observed scattering features such as rainbow positions, integral cross sections, and relative vibrational energy transfers. A comparison with the earlier theoretical study carried out on the semiempirical surfaces (diatomics in molecules) is also made to illustrate the reliability of the potential energy surfaces used in the present work.     

Accuracy of recent potential energy surfaces for the He-N2 interaction. II. Molecular beam scattering and bulk gas relaxation phenomena

A new semiempirical exchange-Coulomb model potential energy surface for the N(2)-He interaction was reported recently [A. K. Dham et al., J. Chem. Phys. 127, 054302 (2007)] and, using it, the temperature dependence of bulk gas properties of N(2)-He mixtures, such as the second virial coefficient and traditional transport phenomena, most of which depend primarily on the isotropic component of the interaction potential energy surface, was determined. Values of these properties, along with values calculated using two high-quality ab initio potential energy surfaces [C.-H. Hu and A. J. Thakkar, J. Chem. Phys. 104, 2541 (1996); K. Patel et al., ibid 119, 909 (2003)] were compared critically to available experimental data. The present paper reports on the ability of the same three potential energy surfaces to predict state-to-state and total differential cross sections, total integral cross sections, and the temperature dependence of bulk gas relaxation phenomena (including magnetic field effects on transport coefficients). While all three potential energy surfaces give total differential and higher speed integral scattering results that fall within the experimental uncertainties, integral scattering results and state-to-state differential cross section measurements consistently exceed the calculated values. All three surfaces give similar agreement with the relaxation properties of N(2)-He binary mixtures, with the semiempirical exchange-Coulomb model potential energy surface giving slightly better overall agreement with experiment than the two ab initio potential energy surfaces.     

Communication: state-to-state differential cross sections for H2O(B̃) photodissociation

Quantum state-to-state differential cross sections, along with the absorption spectrum and product internal state distributions, have been calculated for the photodissociation of H(2)O in its B band on a new set of ab initio potential energy surfaces in a diabatic representation. The theoretical attributes are in good agreement with the recent experimental data, shedding light on the non-adiabatic dissociation dynamics.     

Communication: Mapping water collisions for interstellar space conditions

We report a joint experimental and theoretical study that directly tests the quality of the potential energy surfaces used to calculate energy changing cross sections of water in collision with helium and molecular hydrogen, at conditions relevant for astrophysics. Fully state-to-state differential cross sections are measured for H(2)O-He and H(2)O-H(2) collisions at 429 and 575?cm(-1) collision energy, respectively. We compare these differential cross sections with theoretical ones for H(2)O+H(2) derived from state-of-the-art potential energy surfaces [P. Valiron et al., J. Chem. Phys. 129, 134306 (2008)] and quantum scattering calculations. This detailed comparison forms a stringent test of the validity of astrophysics calculations for energy changing rates in water. The agreement between theory and experiment is striking for most of the state-to-state differential cross sections measured.     

State-to-state differential and relative integral cross sections for rotationally inelastic scattering of H2O by hydrogen

State-to-state differential cross sections (DCSs) for rotationally inelastic scattering of H(2)O by H(2) have been measured at 71.2 meV (574 cm(-1)) and 44.8 meV (361 cm(-1)) collision energy using crossed molecular beams combined with velocity map imaging. A molecular beam containing variable compositions of the (J = 0, 1, 2) rotational states of hydrogen collides with a molecular beam of argon seeded with water vapor that is cooled by supersonic expansion to its lowest para or ortho rotational levels (J(KaKc) = 0(00) and 1(01), respectively). Angular speed distributions of fully specified rotationally excited final states are obtained using velocity map imaging. Relative integral cross sections are obtained by integrating the DCSs taken with the same experimental conditions. Experimental state-specific DCSs are compared with predictions from fully quantum scattering calculations on the most complete H(2)O-H(2) potential energy surface. Comparison of relative total cross sections and state-specific DCSs show excellent agreement with theory in almost all details.     

Elastic/inelastic and charge transfer collisions of H++H2 at collision energies of 4.67, 6, 7.3, and 10 eV

Quantum mechanical studies of vibrational and rotational state-resolved differential cross sections, integral cross sections, and transition probabilities for both the elastic/inelastic and charge transfer processes have been carried out at collision energies of 4.67, 6, 7.3, and 10 eV using the vibrational close-coupling rotational infinite-order sudden approach. The dynamics has been performed employing our newly obtained quasidiabatic potential energy surfaces which were generated using ab initio procedures and Dunning's correlation-consistent-polarized quadrupole zeta basis set. The present theoretical results for elastic/inelastic processes provide an overall excellent agreement with the available experimental data and they are also found to be almost similar to that obtained in earlier theoretical results using the ground electronic potential energy surface, lending credence to the accuracy and reliability of the quasidiabatic potential energy surfaces. The results for the complementary charge transfer processes are also presented at these energies.     

Quasiclassical trajectory studies of H(D)+HBr(DBr) abstraction and exchange reactions

The abstraction and exchange reaction dynamics for H(D)+HBr(DBr) systems have been investigated on three LEPS potential-energy surfaces whose features are in accord with the surface topography suggested by recent molecular-beam and thermal experiments (abstraction barrier less than 1.0 kcal/mole, exchange reaction barriers of =5.0 kcal/mole, and no attractive wells with a depth greater than 0.209 kcal/mole). The surfaces differ primarily in the magnitude of the abstraction barrier which varies from 0.19 to 1.01 kcal/mole. Reaction cross sections have been computed on each surface as a function of relative collision energy from the results of 139000 quasiclassical trajectoris. Comparison of these results with measured relative abstraction cross sections suggests that the true abstraction barrier is very small, perhaps between 0.0 and 0.25 kcal/mole. However, thermal rate coefficients computed on the - best- surface at 300 K are about a factor of 2 larger than the most recently measured values. The calculated (H,D)/(D,H) isotope ratio at 300 K lies between the two reported experimental results. The computed thermal activation energy for abstraction is 835 cal/mole, which is in good agreement with a very early measurements but a factor of 2.5 less than the most recently reported experimental result. These results suggest that the molecular-beam and thermal rate measurements are inconsistent. The average fraction of the available energy which is partitioned into internal product modes <f_E> is found to be nearly independent of relative collision energy and the small topographical differences present in the potential surfaces used in these calculations. We find <f_E> = 0.40. In all reactions, the differential scattering cross sections are peaked in the backward direction for the molecular products, indicating a rebound mechanism.     

He-N2转动非弹性碰撞的理论研究

用CC方法计算了在BTT势能面上碰撞能为27.3meV下He-N₂转动非弹性碰撞截面.研究表明,总的微分碰撞截面与Faubel等的实验结果相似,而态-态微分碰撞截面与实验结果符合欠佳,这与Bowers等的预言一致,     

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.     

Elastic scattering and rotational excitation of nitrogen molecules by sodium atoms

A quantal study of the rotational excitation of nitrogen molecules by sodium atoms is carried out. We present the two-dimensional potential energy surface of the NaN(2) complex, with the N(2) molecule treated as a rigid rotor. The interaction potential is computed using the spin unrestricted coupled-cluster method with single, double, and perturbative triple excitations (UCCSD(T)). The long-range part of the potential is constructed from the dynamic electric dipole polarizabilities of Na and N(2). The total, differential, and momentum transfer cross sections for rotationally elastic and inelastic transitions are calculated using the close-coupling approach for energies between 5 cm(-1) and 1500 cm(-1). The collisional and momentum transfer rate coefficients are calculated for temperatures between 100 K and 300 K, corresponding to the conditions under which Na-N(2) collisions occur in the mesosphere.     

Cold heteromolecular dipolar collisions

Cold molecules promise to reveal a rich set of novel collision dynamics in the low-energy regime. By combining for the first time the techniques of Stark deceleration, magnetic trapping, and cryogenic buffer gas cooling, we present the first experimental observation of cold collisions between two different species of state-selected neutral polar molecules. This has enabled an absolute measurement of the total trap loss cross sections between OH and ND(3) at a mean collision energy of 3.6 cm(-1) (5 K). Due to the dipolar interaction, the total cross section increases upon application of an external polarizing electric field. Cross sections computed from ab initio potential energy surfaces are in agreement with the measured value at zero external electric field. The theory presented here represents the first such analysis of collisions between a (2)Π radical and a closed-shell polyatomic molecule.     

Theory of the photodissociation of ozone in the Hartley continuum; effect of vibrational excitation and O(1D) atom velocity distribution

The effect of vibrational excitation on the photodissociation cross section of ozone in the Hartley continuum is examined. The calculations make use of newly computed potential energy and transition dipole moment surfaces. The initial vibrational states of the ozone are computed using grid based techniques and the first few ab initio computed vibrational energy level spacings agree to within 10 cm(-1) with experimental values. The computed total absorption cross sections arising from different initial vibrational states of ozone are discussed in the light of the nature of the transition dipole moment surface. The computed cross section for excitation from the ground vibrational-rotational state is in good agreement with the experimentally measured cross section. Excitation of the asymmetric stretching vibration of ozone has a marked effect on both the form and magnitude of the photodissociation cross section. The velocity distributions of highly reactive O(1D) atoms arising from the photodissociation process in different wavelength ranges is also presented. The results show that the O(1D) atoms travel with a most probable translational velocity of 2.030 km s(-1) corresponding to a translational energy of 0.342 eV or 33.0 kJ mol(-1).     

Scattering of N(2)O on electron impact over an extensive energy range (0.1 eV-2000 eV)

We report electron impact total cross sections, Q(T), for e-N(2)O scattering over an extensive range of impact energies approximately from 0.1 eV to 2000 eV. We employ an ab initio calculation using R-matrix formalism below the ionization threshold of the target and above it we use the well established spherical complex optical potential to compute the cross sections. Total cross section is obtained as a sum of total elastic and total electronic excitation cross sections below the ionization threshold and above the ionization threshold as a sum of total elastic and total inelastic cross sections. Ample cross section data for e-N(2)O scattering are available at low impact energies and hence meaningful comparisons are made. Good agreement is observed with the available theoretical as well as experimental results over the entire energy range studied here.     

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).     

Quasiclassical trajectory study of the Cl + Hl → HCl + I reaction

Monte Carlo quasiclassical trajectory calculations have been carried out for the reaction Cl + Hl → HCl + I for 300, 1000, and 2000 K. A semi-empirical potential-energy surface (London equation) was obtained by “transfering” parameters from surfaces computed for other reaction systems. The computed results are in general accord with experimental measurements. Thermal rate coefficients, differential scattering cross sections, and product vibrational and rotational distributions were computed for the three temperatures. Angular scattering distributions are in agreement with experiment only at elevated temperatures.     

Resonances in rotationally inelastic scattering of OH(X2Π) with helium and neon

We present detailed calculations on resonances in rotationally and spin-orbit inelastic scattering of OH (X(2)Π, j = 3/2, F(1), f) radicals with He and Ne atoms. We calculate new ab initio potential energy surfaces for OH-He, and the cross sections derived from these surfaces compare well with the recent crossed beam scattering experiment of Kirste et al. [Phys. Rev. A 82, 042717 (2010)]. We identify both shape and Feshbach resonances in the integral and differential state-to-state scattering cross sections, and we discuss the prospects for experimentally observing scattering resonances using Stark decelerated beams of OH radicals.     

Total (elastic + inelastic) cross sections for electron scattering with bound and free germanium and lead atoms

Spherical complex optical potential (SCOP) approach has been used to compute the differential, total (elastic + inelastic) and momentum transfer cross sections for electrons scattering from the bound and free germanium and lead atoms in the energy range from 100–5000 eV. We find that the present calculated differential scattering cross sections (DCS) exhibit all important features (such as forward peaking, dip at middle angles and enhanced backward scattering) observed in other theoretical calculations and experimental measurements. The effect of absorption potential is generally to reduce the elastic cross section.     

Elastic and inelastic cross sections for low-energy electron collisions with pyrimidine

We present theoretical elastic and electronic excitation cross sections and experimental electronic excitation cross sections for electron collisions with pyrimidine. We use the R-matrix method to determine elastic integral and differential cross sections and integral inelastic cross sections for energies up to 15 eV. The experimental inelastic cross sections have been determined in the 15-50 eV impact energy range. Typically, there is quite reasonable agreement between the theoretical and experimental integral inelastic cross sections. Calculated elastic cross sections agree very well with prior results.     

Differential Cross Sections for the F + H2 Reaction: A Comparison of Classical Trajectory Results for Two Potential Energy Surfaces

Classical trajectories were calculated for the F + H₂ reaction over two potential energy surfaces: (1) the well known Muckerman 5 surface (Theoretical Chemistry: Advances and Perspectives 1981 , 6A, 1) and (2) the recent surface of Stark and Werner (J. Chem. Phys. 1996 , 104, 6515). Integral cross sections, state specified cross sections, differential cross sections and product energy distributions were calculated for the two surfaces. Since the methods for calculating the trajectories and expressing differential cross sections were identical for both surfaces, the rather substantial differences in the results are clearly due to differences in the potential surfaces. The results are discussed in terms of the special characteristics of the two surfaces.     

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.