The H—H+, H+—H+ and H—H fragmentation in the collision-induced dissociation of H 2 + ions

The collision-induced dissociation of 10 keV H ₂ ⁺ ions incident on H₂ has been studied in this paper. Total cross sections and angle distributions for the H⁺-H, H⁺-H⁺ and H-H fragmentations are given. Distributions over both angle and velocity have been measured for the H-H⁺ and H-H fragmentation.     

Influence of reagent vibration on the stereodynamics of the Li + HF → LiF + H reaction

We investigate the influence of reagent vibration on the stereodynamics of the title reaction by the quasi-classical trajectory on the Aguado-Paniagua2-potential energy surface developed by Aguado et al. (J. Chem. Phys. 1997 106 1013). The cross sections and reaction probability as functions of the reagent vibration are calculated in the centre-of-mass frame. The product angular distributions of p(θ_r), p(φ_r), and p(θ_r, φ_r), which reflect the vector correlation, are also presented and discussed. The results indicate that the vector properties are sensitively affected by the vibrational excitation.     

Isotopic Effects on Stereodynamics of the C~+ + H_2→CH~+ + H Reaction

The effects of isotope substitution on stereodynamic properties for the reactions C~+ + H_2/HD/HT →CH~+ + H/D/T have been studied applying a quasi classical trajectory method occurring on the new ground state CH_2~+ potential energy surface [J. Chem. Phys. 142(2015) 124302]. In the center of mass coordinates applying the quasi classical trajectory method to investigate the orientation and the alignment of the product molecule. Differential cross section and three angle distribution functions P(θ_r), P(ф_r), P(θ_r, ф_r) on the potential energy surface that fixed the collision energy with a value is 40 kcal/mol have been studied. The isotope effect becomes more and more important with the reagent molecules H_2 changing into HD and HT. P(θ_r, ф_r) as the joint probability density function of both polar angles θ_r and ф_r, which can illustrate more detailed dynamics information. The isotope effect is obvious influence on the properties of stereodynamics in the reactions of C~+ + H_2/HD/HT → CH~+ + H/D/T.     

Quantum State-Resolved Nonadiabatic Dynamics of the H+NaF→Na+HF Reaction

<正>The H+NaF reaction is investigated at the quantum state-resolved level using the time-dependent wavepacket method based on a set of accurate diabatic potential energy surfaces. Oscillatory structures in the total reaction probability indicate the presence of the short-lived intermediate complex,     

The collision energy effect on the stereodynamics of the Ca + HCl→CaCl + H reaction

The stereodynamics of the reaction of Ca + HCl are calculated at three different collision energies based on the potential energy surface [Verbockhaven G et al. 2005 J. Chem. Phys. 122 204307] using quasi-classical trajectory theory. The polarization-dependent differential cross sections (PDDCSs) (2π/σ )(dσ 00 /dω t ), (2π/σ )(dσ 20 /dωt ), (2π/σ )(dσ 22+ /dωt ), (2π/σ )(dσ 21 /dω t ) and the distributions of P(θ r ), P(φr ), and P(θr ,φr ) are calculated. The results indicate that the rotational polarization of the CaCl product presents different characteristics for the different collision energies, and the effects of the collision energy on the vector potential, including the alignment, orientation, and PDDCSs, are not obvious.     

Calculation of H+-ranges and H+-range stragglings in the energy region 1–1000 keV

The use of various approximations in calculating proton projected ranges has been studied by the analytical and the Monte Carlo methods. A correction is presented for the projected ranges given in the compilation (Andersen and Ziegler: Hydrogen Stopping Powers and Ranges in All Elements). The greatest correction factors at 1, 10, 100 and 1000 keV are 3.5, 2.1, 1.4 and 1.2, respectively. The corrections result from the inclusion of the tabulated electronic stopping power values in the calculation of the projected ránge to the total range ratio and from the estimation of the effect of the reflection. The Monte Carlo calculations show the electronic straggling to be a remarkable factor in the width of the proton range distributions at reduced energies larger than of the order of 100.     

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.     

A study of π states of H2 + in the one centre approach

The statistical theory of the elastic constants of nematic liquid crystals is applied to detailed calculations based on well-defined approximations for the direct correlation function of Ornstein and Zernike and for the singlet orientational distribution. The model of hard spherocylinders with superimposed r ^-6 attraction modulated by a Maier-Saupe P ₂(cos ?_{1 2}) term, is used. The dependence on temperature, on the order parameter and on the length to breadth ratio, of the reduced elastic constants K* _i (i=1, 2, 3), is discussed in some detail and comparison with experiment is included.     

A study of the ground states of CaC2H2+,CaC2D2+ and CaC2H4+

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Higher rotational lines in the ν2 fundamental of the H3+ molecular ion

By use of a new high-pressure hollow-cathode discharge cell and a Fourier transform spectrometer, many lines of the ν₂ fundamental band of H₃⁺ are observed in emission. These lines are discriminated from those of other species by pressure labeling, in which the relative intensities are studied as functions of the H₂ gas pressure in the cell. The H₃⁺ lines are found to persist to higher pressures than those of H atoms or H₂ or H₃ molecules. Practically all of the previously known lines of H₃⁺ are observed with this cell, and the measurements are extended to higher J because of the high rotational temperature of the H₃⁺. Absorption measurements of some high-J lines were also performed in this new cell. Altogether 113 lines of the ν₂ band of H₃⁺ with J′_max = 10 have been assigned, and 111 of them are fitted to 0.0654 cm⁻¹ with a 29-parameter effective Hamiltonian that uses a Padé formulation of the centrifugal distortion effects. Many of the higher rotational levels of ν₂ are affected by a Birss resonance with levels of ν₁. The fitted values ν₁ = 3175.0 cm⁻¹ and α₁₂ = 1.377 cm⁻¹ for the vibrational frequency and perturbation parameter are in reasonable agreement with ab initio values. Alternative fits using a vibration-rotation supermatrix model with a limited number of independent matrix elements are consistent with these assignments, but the quality of these fits degrades rapidly with increasing J′_max because the model does not describe centrifugal effects accurately.     

Quasiclassical calculation of the chemical reaction Ba+C3H7Br→BaBr+C3H7

The quasi-classical trajectory (QCT) method based on extended the London-Eyring-Polanyi-Sato potential energy surface is used to investigate the product vibrational distribution, angular distribution and angle resolved kinetic distribution of the reaction Ba+C₃H₇ Br→ BaBr+C₃H₇ at 2.58 kcal/mol. The calculated results show that the product BaBr vibrational distribution is quite hot, the vibrational population peaks are located at ν= 12, and the angular product distribution tends to backward scattering. The calculated angle resolved kinetic distribution shows that the kinetic distribution is obviously related to angle. The QCT results are always qualitatively acceptable and sometimes even quantitatively.     

High Resolution Crossed Beams Scattering Study of the F+HD→DF+H Reaction

采用高分辨的氢原子里德堡态标识的飞行时间谱技术,对F+HD→DF+H反应进行了交叉分子束研究. 在2.51～5.60 kJ/mol的8个碰撞能下,测得了部分转动态分辨的微分截面. 实验结果显示,反应产物角分布表现出显著的后向散射,随着碰撞能的提高,角分布会逐渐变宽. 确定了产物振动态分支比随碰撞能变化的关系. 结果显示产物DF表现出高度振动态反转布居,其中DF(v′=3)态是布居数最高的产物态,在3.97 kJ/mol以上还探测到产物DF(v′=1)的信号.     

Ab initio dynamics of the He + H+ 2 → HeH+ +H reaction: a new potential energy surface and quantum mechanical cross-sections

The reaction He + H⁺ ₂(v,j = 0) → HeH⁺(v′ = 0, j′) for v = 0, 1,2 and 3 and for scattering energies near the threshold (0.95–1.15 eV) has been studied by calculating ab initio points at MRCI level and ‘exact’ integral quantum reactive cross-sections. More than 1400 nuclear geometries have been chosen to cover the most important regions for the dynamics, an extended set of points being taken directly on a hyperspherical coordinate grid. A many-body expansion with a large number of terms permits an accurate analytical representation of the potential energy surface with a root-mean-square deviation <12meV. The hyperquantization algorithm has been extended to obtain quantum mechanical integral cross-sections which are compared with previous calculations and with experimental results.     

Beyond the Monchick–Mason approximation: the mobility of Li+ Ions in H2

The Monchick–Mason approximation for the calculation of the transport coefficients of atomic ions in diatomic gases is extended in a manner that allows comparison of theoretical and experimental mobilities of gaseous ions to serve as quantitative tests of the accuracy of the ab initio, angle- and position-dependent interaction potentials used in the calculations. The feasibility of this procedure is demonstrated with Li⁺ in H₂.     

Study of the ν2 + ν10 Hybrid Band of the Trans-C2H2D2 Molecule

Russian Physics Journal - The ν2 + ν10 (Bu) hybrid band of the trans-C2H2D2 molecule in the region 2100–2300 cm–1 is studied for the first time. The spectrum has been analyzed...     

Quasi-classical trajectory study of collision energy effect on the stereodynamics of H + Br O → O + HBr reaction

Quasi-classical trajectory(QCT) studies on the stereodynamics of H + Br O → O + HBr reaction have been performed on the X1A′state of ab initio potential energy surface by Peterson [Peterson K A 2000 J. Chem. Phys. 113 4598] in a collision energy range from 0 kcal/mol to 6 kcal/mol. Two of the polarization-dependent generalized differential cross sections(PDDCSs),(2π /σ)( dσ00/ dωt)(PDDCS00) and(2π /σ)( dσ20/ dωt)(PDDCS20) are considered. The rotational polarizations of these products show sensitive behaviors to the calculated collision energy range. Furthermore, in order to gain more knowledge about vector correlations, the product angular distribution, P(θr), and the dihedral angle, P(φr),are calculated, and the results indicate that both the rotational alignment and orientation of the product are enhanced as collision energy increases.     

High resolution study of the ν5 + ν12 band of C2H4

The combination band ν₅ + ν₁₂ of ethylene, C₂H₄, has been recorded for the first time with a high resolution Fourier transform spectrometer Bruker IFS 125HR. Assignments of transitions and preliminary rotational analysis are made. Two models (Hamiltonian of the isolated vibrational state and Hamiltonian that takes into account resonance interactions) are used. Influence of the local resonance interactions on the parameters and reproduction power of the models is discussed.     

Force and density study of the chemical reaction process OH2+H+→OH3 +

The force and density origin of the ionic reaction process OH₂+H⁺→OH₃ ⁺ is studied on the basis of the electrostatic force theory. In order to obtain reliable results, we have used the floating AO wavefunction (with minimal basis) which satisfies the Hellmann-Feynman theorem for the approaching proton. Accuracies of the results of the ordinary nuclear-centred AO wavefunction (with minimal basis plus polarization functions on hydrogen atoms) have been also examined. It is shown that the predominant origin of the driving force is the atomic dipole force which is caused by the transfer of the lone-pair density of OH₂ into the atomic region of H⁺ and the succeeding inward polarization of the transferred electron density. The exchange force due to density accumulation in the forming O-H⁺ bond region is of secondary importance. This is in contrast with the previous results for the radical reaction processes. The present reaction may be regarded as the transformation of the lone pair into the bond pair.     

Effects of the dielectric discontinuity on the photodetachment of H− ion

Using the closed orbit theory, we studied the effects of dielectric discontinuity on the photodetachment of H^? ions. The photodetachment cross-section of H^? in a medium with dielectric discontinuity was derived and calculated. The results have shown that the relative dielectric constants of the medium have a significant influence on the photodetachment of H^?. If H^? is kept in a medium with a relative small dielectric constant, the photodetachment cross-section of H^? becomes oscillating only in a small region above the ionization threshold. However, if H^? is kept in a medium with a relative large dielectric constant, the oscillation in the photodetachment cross-section becomes much stronger. Besides, the distance between H^? and the dielectric dividing interface also influences the photodetachment of H^?. For a given dielectric medium, the oscillation in the cross-section decreased with increasing distance between H^? and the dielectric dividing interface. Therefore, we can control the photodetachment of a negative ion by changing the dielectric constant and the ion–interface distance. This study provides a new understanding of the photodetachment process of negative ions in the presence of a dielectric medium.