Reaction mechanism of D + ND→N + D_2 and its state-to-state quantum dynamics

The quantum state-to-state calculations of the D + ND→N + D_2 reaction are performed on a potential energy surface of 4 A' state. The state-resolved integral and differential cross sections and product state distributions are calculated and discussed. It is found that the rotational distribution, rather than the vibrational distribution, of the product has an obvious inversion. Due to the fact that it is a small-impact-parameter collision, its product D_2 is mainly dominated by rebound mechanism, which can lead to backward scattering at low collision energy. As the collision energy increases, the forward scattering and sideward scattering begin to appear. In addition, the backward collision is also found to happen at high collision energy, through which we can know that both the rebound mechanism and stripping mechanism exist at high collision energy.     

State-to-state quantum dynamics of the N(~4S)+H_2(X~1Σ~+) → NH(X~3Σ~-)+H(~2S) reaction and its reaction mechanism analysis

Quantum state-to-state dynamics of the N(4S) + H-2(X1+Σ) → NH(X3Σ) + H(2S) reaction is reported in an accurate novel potential energy surface constructed by Zhai et al.(2011 J. Chem. Phys. 135 104314). The time-dependent wave packet method, which is implemented on graphics processing units, is used to calculate the differential cross sections. The influences of the collision energy on the product state-resolved integral cross sections and total differential cross sections are calculated and discussed. It is found that the products NH are predominated by the backward scattering due to the small impact parameter collisions, with only minor components being forward and sideways scattered, and have an inverted rotational distribution and no inversion in vibrational distributions; both rebound and stripping mechanisms exist in the case of high collision energies.     

Mechanism analysis of reaction S~+(~2D)+H_2(X~1Σ_g~+) → SH~+(X~3Σ~-) + H(~2S) based on the quantum state-to-state dynamics

We present a state-to-state dynamical calculation on the reaction S~++ H_2→ SH~+ +H based on an accurate ~X2 A~″ potential surface. Some reaction properties, such as reaction probability, integral cross sections, product distribution, etc.,are found to be those with characteristics of an indirect reaction. The oscillating structures appearing in reaction probability versus collision energy are considered to be the consequence of the deep potential well in the reaction. The comparison of the present total integral cross sections with the previous quasi-classical trajectory results shows that the quantum effect is more important at low collision energies. In addition, the quantum number inversion in the rotational distribution of the product is regarded as the result of the heavy–light–light mass combination, which is not effective for the vibrational excitation. For the collision energies considered, the product differential cross sections of the title reaction are mainly concentrated in the forward and backward regions, which suggests that there is a long-life intermediate complex in the reaction process.     

Vector correlations study of the reaction N(~2D) + H_2(X~1Σ_g~+) →NH(a~1?) + H(~2S) with different collision energies and reagent vibration excitations

Vector correlations of the reaction N(2D)+ H2(X1Σ+g) → NH(a1?)+ H(2S) are studied based on a recent DMBESEC PES for the first excited state of NH2[J. Phys. Chem. A 114 9644(2010)] by using a quasi-classical trajectory method.The effects of collision energy and the reagent initial vibrational excitation on cross section and product polarization are investigated for v = 0–5 and j = 0 states in a wide collision energy range(10–50 kcal/mol). The integral cross section could be increased by H2 vibration excitation remarkably based on the DMBE-SEC PES. The different phenomena of differential cross sections with different collision energies and reagent vibration excitations are explained. Particularly,the NH molecules are scattered mainly in the backward hemisphere at low vibration quantum number and evolve from backward to forward direction with increasing vibration quantum number, which could be explained by the fact that the vibrational excitation enlarges the H–H distance in the entrance channel, thus enhancing the probability of collision between N atom and H atom. A further study on product polarization demonstrates that the collision energy and vibrational excitation of the reagent remarkably influence the distributions of P(θr), P(φr), and P(θr, φr).     

Quasi-classical trajectory study of H+LiH(v=0,1,2,j=0)→Li+H_2 reaction on a new global potential energy surface

Quasi-classical trajectory(QCT) calculations are reported for the H+LiH(v = 0–2, j = 0)→Li+H_2 reaction on a new ground electronic state global potential energy surface(PES) of the LiH_2 system. Reaction probability and integral cross sections(ICSs) are calculated for collision energies in the range of 0 eV–0.5 eV. Reasonable agreement is found in the comparison between present results and previous available theoretical results. We carried out statistical analyses with all the trajectories and found two main distinct reaction mechanisms in the collision process, in which the stripping mechanism(i.e., without roaming process) is dominated over the collision energy range. The polarization dependent differential cross sections(PDDCSs) indicate that forward scattering dominates the reaction due to the dominated mechanism. Furthermore,the reactant vibration leads to a reduction of the reactivity because of the barrierless and attractive features of PES and mass combination of the system.     

Non-adiabatic quantum dynamical studies of Na(3p) + HD(v = 1, j5) = 0)→NaH/NaD + D/H reaction

Non-adiabatic dynamical calculations are carried out for the Na(3 p)+HD(ν = 1, j = 0)→NaH/NaD+D/H reaction on the diabatic potential energy surfaces of Wang et al.(Sci. Rep. 2018, 8, 17960) by using the time-dependent wave packet method. The state-to-state integral cross sections and differential cross sections of two reaction channels(NaH/NaD+D/H)are calculated for collision energy up to 0.4 eV. The cross section branching ratio indicates that the dominant reaction channel changes from NaD+H to NaH+D when the collision energy is larger than 0.227 eV. The products from two reaction channels both prefer to form in vibrationally cold but rotationally hot states, and they both tend to forward scattering.     

Effect of reagent vibrational excitation and isotope substitution on the stereo-dynamics of the Ba+HF→BaF+H reaction

Based on an extended London-Eyring-Polanyi-Sato (LEPS) potential energy surface (PES), the Ba + HF reaction has been studied by the quasi-classical trajectory (QCT) method. The reaction integral cross section as a function of collision energy for the Ba + HF → BaF + H reaction is presented and the influence of isotope substitution on the differential cross sections (DCSs) and alignments of the product's rotational angular momentum have also been studied. The results suggest that the integral cross sections increase with increasing collision energy, and the vibrational excitation of the reagent has great influence on the DCS. In addition, the product's rotational polarization is very strong as a result of heavy-heavy-light (HHL) mass combination, and the distinct effect of isotope substitution on the stereodynamics is also revealed.     

Differential, elastic integral and moment transfer cross sections for electron scattering from N2 at intermediate- and high-energies

A complex optical model potential modified by incorporating the concept of bonded atom, with the overlapping effect of electron clouds between two atoms in a molecule taken into consideration, is firstly employed to calculate the differential cross sections, elastic integral cross sections, and moment transfer cross sections for electron scattering from molecular nitrogen over the energy range 300—1000eV by using additivity rule model at Hartree—Fock level. The bonded-atom concept is used in the study of the complex optical model potential composed of static, exchange, correlation polarization and absorption contributions. The calculated quantitative molecular differential cross sections, elastic integral cross sections, and moment transfer cross sections are compared with the experimental and theoretical ones wherever available, and they are found to be in good agreement with each other. It is shown that the additivity rule model together with the complex optical model potential modified by incorporating the concept of bonded atom is completely suitable for the calculations of differential cross section, elastic integral cross section and moment transfer cross section over the intermediate- and high-energy ranges.     

Stereodynamics in reaction O（1D） ＋ CH4 〉OH ＋ CH3

A theoretical study of the stereodynamics for reaction O(1D) + CH4→OH + CH3 has been carried out using the quasiclassical trajectory method(QCT) on a potential energy surface structured by Gonzalez et al. The integral cross sections(ICSs), differential cross sections(DCSs) and product rotational angular momentum polarization have been calculated. With the collision energy increasing, the ICS decreases. There is no threshold energy, because no barrier is found on the minimum energy path. The DCS results show that the backward and forward scatterings exist at the same time. With the collision energy increasing, the dominant rotation of the product changes from the right-handed direction to the left-handed direction in planes parallel to the scattering plane. In the isotopic effect study, the decrease of the mass factor weakens the polarization degree of the rotational angular momentum vectors of the products.     

Effects of a reagent＇s rotational and vibrational excitations on reactionO（3p）＋ H2（v=0, 3, j = 0, 3, 5, 7, 9, 12, 15） → OH ＋ H

To investigate the effect of a reagent’s rotational and vibrational excitations on the stereo-dynamics of the reaction product, the title reaction is theoretically simulated using the quasi-classical trajectory (QCT) method on the 3 A and 3 A potential energy surfaces (PESs). The reaction cross section is considered as the only scalar property in this work at four different collision energies. Furthermore the vector properties including two polarization-dependent differential cross sections (PDDCSs), the angular distributions of product’ rotational momentum are discussed at one fixed collision energy. Effects of reagents’ rotational excitation on the reaction do exist regularly.     

Positron total cross sections for collisions with N_2 and CO_2 at 30-3000 eV

The total (elastic plus inelastic) cross sections for positron scattering from N2 and CO2 over the incident energy range from 30 to 3000eV are calculated using the additivity rule model at Hartree-Fock level. A complex optical model potential modified by incorporating the concept of bonded atom, which takes into account the overlapping effect of electron clouds between two atoms in a molecule, is employed to calculate the total cross section of positron-molecule scattering. The calculated total cross sections are in good agreement with those reported by experiments and other theories over a wide energy range.     

Positron total cross sections for collisions with N2 and CO2 at 30-3000 eV

The total (elastic plus inelastic) cross sections for positron scattering from N2 and CO2 over the incident energy range from 30 to 3000eV are calculated using the additivity rule model at Hartree-Fock level.A complex optical model potential modified by incorporating the concept of bonded atom, which takes into account the overlapping effect of electron clouds between two atoms in a molecule, is employed to calculate the total cross section of positron-molecule scattering. The calculated total cross sections are in good agreement with those reported by experiments and other theories over a wide energy range.     

Quasi-classical trajectory investigation on the stereodynamics of Li ＋ DF（v=1-6,j=0）→LiF＋D reaction

In this paper, the stereodynamics of Li ＋ DF → Li F ＋ D reaction is investigated by the quasi-classical trajectory（QCT）method on the ^2A＇ potential energy surface（PES） at a relatively low collision energy of 8.76 kcal/mol. The scalar properties of the title reaction such as reaction probability and cross section are studied with vibrational quantum number of v = 1–6. The product angular distributions P（θr） and P（φr） are presented in the same vibrational level range. Moreover, two polarization-dependent generalized differential cross sections（PDDCSs）, i.e., the PDDCS00 and PDDCS22＋are calculated as well. These stereodynamical results demonstrate sensitive behaviors to the vibrational quantum numbers.     

Influence of electron correlations on double-capture process in proton helium collisions

The first-order correct-boundary Coulomb–Born distorted-wave approximation is used to study the double-electron capture by protons from the ground-state helium atoms at intermediate and high impact energies. The differential double capture cross sections are obtained as a function of the projectile scattering angle and the total cross sections as a function of the impact energy. In the considered range of impact energy, our calculation shows that although the results are not so sensitive to the static inter-electronic correlations in the initial channel, the strong final-state correlations have a large effect on the magnitudes of the double capture cross sections. The calculated differential and integral cross sections are compared with their available experimental values. The comparison shows a good agreement between the present calculations and the measurements. The comparison of the integral cross sections shows that the present approach is compatible with other theories.     

State-to-state dynamics of reactions H+DH'(v=0,j=0)→HH'(v',j')+D/HD(v',j')+H'with time-dependent quantum wave packet method

State-to-state time-dependent quantum dynamics calculations have been carried out to study H+DH'→HH'+D/HD+H' reactions on BKMP2 surface.The total integral cross sections of both reactions are in good agreement with earlier theoretical and experimental results,moreover the rotational state-resolved reaction cross sections of H+DH'→HH‘+D at collision energy Ec=0.5 eV are closer to the experimental values than the ones calculated by Chao et al [J.Chem.Phys.117 8341(2002)],which proves the higher precision of the quantum calculation in this work.In addition,the state-to-state dynamics of H+DH'→ HD'+H reaction channel have been discussed in detail,and the differences of the micro-mechanism of the two reaction channels have been revealed and analyzed clearly.     

Stereodynamics study of the exchange reaction O(~3P)+CH_4 →H+OCH_3

A new London-Eyring-Polanyi-Sato potential energy surface is employed in this work to study the stereo properties of the O(3P)+CH4 →H+CH3O reaction in its rovibrationally ground state using the quasiclassical trajectory method(QCT).Our calculations are performed at a range of collision energies,Ec=1.5eV～3.5eV,and the excitation function obtained by the QCT method accords well with the experimental data.The product rotational polarization is calculated,and the product shows a strong rotational polarization in the centre-of-mass coordinate system.The orientation of the product rotational angular momenta is sensitive to the increase in collision energy,and the alignment of the product rotational angular momenta shows some of the properties of the heavy heavy-light mass combination reactions.In the isotopic substituted reaction study,when the H atoms in methane are replaced by D atoms,the rotational polarization is obviously reduced.The polarization-dependent differential cross section is also studied by this QCT calculation to provide detailed information about the rotational alignment and orientation of the product.     

Additivity rule for electron--molecule total cross section calculations at 50--5000eV: a new geometrical approach

Taking into consideration the changes of the geometric shielding effect in a molecule as the energy of incident electrons varies, this paper presents an empirical fraction, which depends on the energy of incident electrons, the target＇s molecular dimension and the atomic and electronic numbers in the molecule. Using this empirical fraction, it proposes a new formulation of the additivity rule. Employing the new additivity rule, it calculates the total cross sections of electron scattering by C2H4, C6H6, C6H14 and C8H18 over the energy range from 50 to 5000eV. In order to exclude the calculation deviations caused by solving the radial Schrodinger equation of electron scattering by atoms, here the atomic cross sections are derived from the experimental total cross section results of simple molecules （H2, O2, CO） via the inversion algorithm. The quantitative total cross sections are compared with those obtained by experiments and other theories, and good agreement is obtained over a wide energy range, even at energy of several tens of eV.     

A typical slow reaction H（2S） ＋ S2（X3∑g） → SH（X2П） ＋S（3P） ona new surface： Quantum dynamics calculations

Quantum dynamics calculations for the title reaction H(2S) + S2(X3-Σg) → SH(X2Π) + S(3P) are performed by using a globally accurate double many-body expansion potential energy surface [J. Phys. Chem. A 115 5274(2011)].The Chebyshev real wave packet propagation method is employed to obtain the dynamical information, such as reaction probability, initial state-specified integral cross section, and thermal rate constant. It is found not only that there is a reaction threshold near 0.7 eV in both reaction probabilities and integral cross section curves, but also that both the probability and cross section increase firstly and then decrease as the collision energy increases. The existence of the resonance structure in both the probability and cross section curves is ascribed to the deep potential well. The calculation of the rate constant reveals that the reaction occurring on the potential energy surface of the ground-state HS2is slow to take place.     

The effect of the rotational excitation of NO on the stereodynamics for the reaction C(~3P)+NO(X~2Π)→CN(X~2Σ~+)+O(~3P)

The stereodynamic properties of the reaction C(3P)+NO(X2Π)→CN(X2Σ+)+O(3P) in different rotational states of reactant NO are studied theoretically by using the quasiclassical trajectory method on 2A' and 2A' potential energy surfaces(PESs) at a collision energy of 0.06 eV.The vector properties in different rotational states on the two surfaces are discussed in detail.The results indicate that the rotational excitation of NO has considerable influence on the stereodynamic property of the reaction occurring on the two surfaces.At the same time,the calculated polarization-dependent differential cross sections(PDDCSs) in different initial rotational states manifest that products are strongly polarized at three scattering angles.     

Quasiclassical trajectory theoretical study on the chemical stereodynamics of the O(~1D)+H_2→OH+H reaction and its isotopic variants (HD,D_2)

The quasiclassical trajectory (QCT) method is used to study stereodynamic information about the reaction O ( 1 D) + H 2 →OH + H on the DK (Dobbyn and Knowles) (1 1 A' ) ab initio potential energy surface (PES). A wide scale of collision energy (E c ) from 0.05 eV to 0.5 eV is considered in the dynamic calculations. To reveal the rovibrational excitation effect, calculations at a collision energy of 0.52 eV are carried out for the v = 0 ～ 5, j = 0 and v = 0, j = 0 ～ 15 initial states. The two popularly used polarization-dependent differential cross sections (PDDCSs), dσ 00 /dω t (0, 0) and dσ 20 /dω t (2, 0), and two angular distributions, P(θ r ) and P( r ) are calculated to obtain an insight into the alignment and the orientation of the product molecules. From the calculations, we can obtain that the alignment of the OH product is weaker at high collision energy and becomes stronger with the increase of initial vibrational level, and it is almost insensitive to the initially rotational excitation. Influences of the mass values of isotopes (HD, D 2 ) on the stereodynamics are also shown and discussed. Comparisons between available theoretical results and experimental results are made and discussed.