Semirigid vibrating rotor target calculation for reaction O(~3P)+CH_4 →CH_3+OH

There are some statistical model codes[1—4] as the evaluation tool that have been long and widely used to set up neutron data library below 20 MeV, which is the most important energy region in the application of nuclear engineering. The emitted particles considered in these codes mentioned above are neutrons, protons, as well as the compos-ite particles, such as deuterons, tritons, 3He and alpha particles. These emitted particles and nuclei can be treated as the nucleon or stable clusters. H…     

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.     

State-to-state dynamics of F(~2P) + HO(~2Π) → O(~3P) + HF(~1Σ~+)reaction on 1~3A〞 potential energy surface

State-to-state time-dependent quantum dynamics calculations are carried out to study F(~2P) + HO(~2Π) → O(~3P) +HF(~1Σ~+) reaction on 1~3A〞 ground potential energy surface(PES). The vibrationally resolved reaction probabilities and the total integral cross section agree well with the previous results. Due to the heavy–light–heavy(HLH) system and the large exoergicity, the obvious vibrational inversion is found in a state-resolved integral cross section. The total differential cross section is found to be forward–backward scattering biased with strong oscillations at energy lower than a threshold of 0.10 eV, which is the indication of the indirect complex-forming mechanism. When the collision energy increases to greater than 0.10 eV, the angular distribution of the product becomes a strong forward scattering, and almost all the products are distributed at θ_t = 0°. This forward-peaked distribution can be attributed to the larger J partial waves and the property of the F atom itself, which make this reaction a direct abstraction process. The state-resolved differential cross sections are basically forward-backward symmetric for v' = 0, 1, and 2 at a collision energy of 0.07 eV; for a collision energy of 0.30 eV,it changes from backward/sideward scattering to forward peaked as v increasing from 0 to 3. These results indicate that the contribution of differential cross sections with more highly vibrational excited states to the total differential cross sections is principal, which further verifies the vibrational inversion in the products.     

A full-dimensional analytical potential energy surface for the F+CH_4→HF+CH_3 reaction

A full-dimensional analytical potential energy surface(APES) for the F + CH4 →HF + CH3 reaction is developed based on 7127 ab initio energy points at the unrestricted coupled-cluster with single,double,and perturbative triple excitations.The correlation-consistent polarized triple-split valence basis set is used.The APES is represented with a many-body expansion containing 239 parameters determined by the least square fitting method.The two-body terms of the APES are fitted by potential energy curves with multi-reference configuration interaction,which can describe the diatomic molecules(CH,H2,HF,and CF) accurately.It is found that the APES can reproduce the geometry and vibrational frequencies of the saddle point better than those available in the literature.The rate constants based on the present APES support the experimental results of Moore et al.[Int.J.Chem.Kin.26,813(1994)].The analytical first-order derivation of energy is also provided,making the present APES convenient and efficient for investigating the title reaction with quasiclassical trajectory calculations.     

The catalytic effects of H2CO3, CH3COOH,HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

The addition reaction of CH₂OO + H₂O → CH₂(OH)OOH without and with X (X = H₂CO₃, CH₃COOH and HCOOH) and H₂O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH₂OO + H₂O → CH₂(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH₂OO···H₂O is favourable one. Water-assisted CH₂OO + H₂O → CH₂(OH)OOH can occur by H₂O moiety of (H₂O)₂ or the whole (H₂O)₂ forming cyclic structure with CH₂OO, where the latter form is more favourable. Because the concentration of H₂CO₃ is unknown, the influence of CH₃COOH, HCOOH and H₂O were calculated within 0–30 km altitude of the Earth's atmosphere. The results calculated within 0–5 km altitude show that H₂O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%–77.26% and 0.04%–1.76%. Within 5–30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%–98.28%. However, compared with the reaction of CH₂OO + HCOOH, the rate of CH₂OO···H₂O + HCOOH is much slower.     

Theoretical prediction of the optimal conditions for observing the stereodynamical vector properties of the C(~3P) + OH(X~2Π) → CO(X~1 Σ~+) + H(~2S) reaction

The best optimal initial reactant state and collision energy for observing the stereodynamical vector properties of the title reaction in the ground electronic state X2A potential energy surface(PES) [Zanchet et al. 2006 J. Phys. Chem. A 110 12017] are theoretically predicted using the quasi-classical trajectory(QCT) method for the first time. The calculated results reveal that the smallest value of the rotational quantum number j, larger vibrational quantum number v, and the lower strength of collision energy should be selected for offering the most obvious picture about the stereodynamical vector properties. Polarization-dependent differential cross sections and the angular momentum alignment distribution, P(θr) and P(Φr) in the center-of-mass frame, are obtained to gain an insight into the alignment and orientation of the product molecules. The rotational angular momentum vector j of CO is aligned to be perpendicular to reagent relative velocity k. The product polarizations align along the y axis, pointing to the positive direction of the y axis. A new method is developed to investigate massive reactions with various initial states and to further study the vector properties of the fundamental reactions in detail.     

The reagent vibrational excitation effect on the stereodynamics of the reaction O(~1D)+HBr→OH+Br

Calculations on the dynamics of the reaction O( 1 D) + HBr → OH + Br are performed on the ab initio potential energy surfaces (PESs) of the ground state given by Peterson Peterson K A J. Chem. Phys. 113 4598 (2000)using the quasiclassical trajectory (QCT) method. The product distribution of the dihedral angle, P (φ r ), and that of the angle between and , P (θ r ), are presented in three dimensions. Moreover, we also investigate the reagent vibrational excitation effects on the two polarization-dependent generalized differential cross sections (PDDCS), PDDCS 00 and PDDCS 20 , in the center-of-mass frame. The results indicate that the vector properties are sensitive to the reagent vibrational quantum number.     

Theoretical study of stereodynamics for the D'+ DS(v=0,j=0) → D'D + S abstraction reaction

Quasiclassical trajectory (QCT) calculations have been performed for the abstraction reaction, D'+ DS(v = 0, j = 0) → D'D + S on a new LZHH potential energy surface (PES) of the adiabatic 3 A electronic state [Lü et al. 2012 J. Chem. Phys. 136 094308]. The collision energy effect on the integral cross section and product polarization are studied over a wide collision energy range from 0.1 to 2.0 eV. The cross sections calculated by the QCT procedure are in good accordance with previous quantum wave packet results. The three angular distribution functions, P(θr), P(φr), and P(θr,φr), together with the four commonly used polarization-dependent differential cross sections ((2π/σ)(dσ00/dωt), (2π/σ)(dσ20/dωt), (2π/σ)(dσ22+/dωt), (2π/σ)(dσ21/dωt)) are obtained to gain insight into the chemical stereodynamics of the title reaction. Influences of the collision energy on the product polarization are exhibited and discussed.     

O (3P) + H2 → OH+H反应的立体动力学研究

用BMS1势能面[Brandão 等, J.Chem.Phys. 121, 8861 (2004)],选取碰撞能为34.6kcal/mol,用准经典轨线方法研究了O ( ) + 反应的立体动力学性质。计算并讨论了k与j'的夹角的分布关系P ( )以及描述k-k'- j'三者关系的二面角分布。（k为反应物速度方向,k'为产物的速度方向,j'为产物的角动量方向） 的峰值在90°附近并且关于90°呈对称性分布,这表明产物角动量的方向与初速度的方向垂直。二面角分布P( )关于散射平面呈反对称性分布,这一结果表明产物的角动量具有强烈的极化效应。另外,我们还研究了振动激发对产物角动量的影响,结果表明产物的矢量性质对反应物的初始振动态非常敏感。     

CH3CH2+O(3P)反应机理的理论研究

利用abinitio方法对CH3CH2+O(3P)反应进行了理论研究,在MP2/6311+G(d,p)水平上优化得到了反应途径上的反应物、中间体、过渡态和产物的几何构型和谐振频率,并在QCISD(T)/6311+G(d,p)水平上进行单点能计算.计算结果表明:CH2O+CH3、CH3CHO+H和CH2CH2+OH是主要反应产物,其中CH2O+CH3主要来自反应通道A1:(R)→IM1→TS3→(A),CH3CHO+H主要来自反应通道B1:(R)→IM1→TS4→(B),CH2CH2+OH主要来自直接抽提反应通道C1和C2:(R)→TS1(TS2)→(C).计算结果同时表明该反应生成CO的通道能垒是非常高的,CO应该不是主要产物.     

Calculated rates for the reactionμ −+He3→H3+ν

The effective Hamiltonian ofMorita andFujii is used to calculate the muon capture rate\(\mathfrak{W}_\mu \) in He³. The calculation is done including and omitting the “weak magnetic interaction” and for positive and negative sign of pseudoscalar coupling. The results are related to the known value offt for the beta decay of the triton. The r.m.s. radius of the charge distribution in He³ is taken to be 1·55 fm rsp. 1·85fm. (The first value follows from the results of the variational calculation ofKikuta, Morita, andYamada, the last value is based on a variational calculation for a potential with a long tailed attractive part.) The capture rates differ by 10% for the two r.m.s. radii. Our result forv _r.m.s.= 1·55 fm deviates slightly from the corresponding result ofWerntz.     

Variability of the atmospheric N2O line (J=3→4)

We analyze the results of observations of the radio emission of atmospheric N₂O in the line J=3→4 at frequency near 100.5 GHz. Observations aimed at monitoring the nitrous oxide content at altitudes h>20 km were performed in Nizhny Novgorod from March to May, 1997. We discover variations of the optical-depth decrement in the line, which can be explained by the redistribution of nitrous oxide over the altitude range h=20–55 km. This assumption does not contradict published data on in-situ measurements of N₂O density at h=5–35 km. Using the obtained data we calculate the rotational-line spectra of atmospheric N₂O. We point out that the measured decrements of the optical depths are greater than the calculated ones. We discuss observations of the N₂O lines in the mm-wave band as a promising method for monitoring the vertical mixing in the atmosphere. N. I. Lobachevsky State University, Nizhny Novgorod, Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 42, No. 10, pp. 933–939, October 1999.     

Time-Dependent Quantum Dynamics of T＋CH4 → CH3＋HT Reaction

Reaction probability, cross section and rate constant are studied for polyatomic reaction T CH4 → CH3 HT using the semirigid vibrating rotor target (SVRT) model. The numerical calculation for the reaction system is carried out using the time-dependent wavepacket method, and the wavepacket is propagated by the splitoperator method. The calculation exhibits a variety of features that can be used for comparison with future experimental investigations. The reaction probability as a function of the translational energy shows slight oscillatory structures, similar to those observed in H abstraction reactions H H2 and H CH4. The comparisons with the H CH4 reaction are described.     

Correlated energy disposal and scattering dynamics of the Cl CD4(ν3 = 2) reaction

Molecular chlorine, methane and helium are co-expanded into the extraction region of a Wiley-McLaren time-of-flight spectrometer. After preparing the first overtone of the antisymmetric stretch (ν3 = 2) with direct IR excitation, the reaction is initiated by photolysing Cl2 with 355 nm light to produce mono-energetic Cl atoms with a translational energy of 0.18 eV. The CD3 and DCl products are state-selectively detected via resonance enhanced multiphoton ionization (REMPI) and analysed with the core-extraction technique. Unusual structure in the 3pz CD3 REMPI spectrum suggests the presence of a previously unobserved transition, which we assign to the stretch-bend combination ( [image omitted]) band. The product correlated energy disposal and the scattering distributions are compared with the same quantities for the Cl + CH4(ν3 = 2) reaction and found to be similar, although subtle differences are observed. The results for the Cl + CD4(ν3 = 2) reaction support a localized chemistry model in which the Cl atom interacts with a single C-D oscillator and leaves the CD3 methyl radical as a spectator.     

Theoretical study of stereodynamics for the O（3P） ＋ H2 → OH ＋ H reaction

This paper employs the quasi-classical trajectory calculations to study the influence of collision energy on the title reaction on the potential energy surface of the ground ³A' triplet state developed by Rogers et al. (J. Phys. Chem. A 2000 104 2308). It calculates the product angular distribution of P(θ_r), P(φ_r) and P(θ_r, φ_r) which reflects vector correlation. The distribution P(θ_r) shows that product rotational angular momentum vectors j' of the products are strongly aligned along the relative velocity direction k. The distribution of P(φ_r) implies a preference for left-handed product rotation in planes parallel to the scattering plane. Four different polarisation-dependent cross-sections are also presented in the centre-of-mass frame. Results indicate that OH is sensitively affected by collision energies of H₂.     

Quantum chemical study of the (Z)-2-penten-1-ol (HOCH2–CH = CHCH2CH3) + OH + O2 reactions

ABSTRACT

The mechanism and products of the reaction of (Z)-2-penten-1-ol [(Z)-PO21] with OH radical in the presence of O₂ have been elucidated by using high-level quantum chemical methods CCSD(T)/6-311+G(d,p)//BH&;HLYP/6-311++G(d,p). The calculations clearly indicate that addition channels contribute maximum to the total reaction and H-abstraction channels can be neglected at temperatures of 220–500 K. The rate constant for the reaction of OH radical with (Z)-PO21 at 298 K is computed to be 1.22 × 10^?10 cm³ molecule^?1 s^?1, which is in stronger agreement with the previously reported experimental values. The kinetic data obtained over the temperature range 220?500 K are used to derive an non-Arrhenius expression: k = 3.69 × 10^?13 × exp(1763.7/T) cm³ molecule^?1 s^?1. For the reaction of (Z)-PO21with OH radical in the presence of O₂, the major primary reaction products found in this study are propanal [CH₃CH₂C(O)H] and glycolaldehyde [HOCH₂C(O)H], whereas formaldehyde [HC(O)H], 2-hydroxybutanal [CH₃CH₂CH(OH)C(O)H] and the epoxide P18 are anticipated to be minor products. The calculated results are consistent with the recent experimental observations.     

P-Odd effects in the γ+He4 → He4 + π0 reaction

P-Odd effects with the elastic photoinformation of neutral pions in He⁴ nuclei are due to the interference of the P-odd amplitude of weak interaction with the P-even amplitude of strong interaction, and originate only for polarized photons. It is shown that close to the reaction threshold P-odd effects should be small. The interference amplitude of the mechanisms corresponding to exchange with a Regge or-pole and a neutral Z-boson at high energies is studied. P-Odd effects in this case increase with increase of energy of the interacting particles and with the square of the imparted momentum. P-Odd effects due to interference of the s ingle-photon and Z-boson mechanisms are also investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 71–76, September, 1978.     

Dynamics of η→3π0 decay

The η→3π⁰ decay was studied with the SND detector at the VEPP-2Me ⁺ e ^? collider. The parameter that describes deviation of the Dalitz plot of events from a uniform distribution was found to be α=?0.010±0.021±0.010.