碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布

采用准经典轨线方法研究了碰撞反应Ca+C2H5Br和Ca+nC3H7Br产物CaBr的内能态分布,计算了产物分子CaBr的平均振动、转动和平动能量以及总可资用能量.结果表明,当碰撞能为7.54kJ/mol时,产物的能量主要为振动能量;随着碰撞能增加,产物的平动能和转动能增加,而振动能略微减小,最可几振动态向较低振动能级移动;反应物分子内能态分布对产物分子的内能态分布影响很小;反应基团越大,产物的振动能占总可资用能量的比例就越高.碰撞反应Ca+C2H5Br和Ca+nC3H7Br均存在两条竞争的反应路径迁移相碰和直接反应路径.前者产生高振动激发态产物CaBr,后者引起C-Br键断裂.当碰撞能增加时,两种反应均倾向于后者.     

Large contribution of deep inelastic processes to reactions of40Ar and48Ca with238U

Differential recoil range distributions have been measured for heavy-reaction products ranging from Te(Z=52) to quasielastic transfer products near the charge and mass of the targets for the reactions of 276 MeV⁴⁸Ca+²³⁸U, 237MeV and 250 MeV⁴⁰Ar+²³⁸U, and 259 MeV⁴⁰Ar+¹⁹⁷Au. The measured recoil range distributions for the⁴⁰Ar+¹⁹⁷Au reaction agree with range distributions calculated from the known projectile-like fragment angular distributions for this reaction. The angular distributions of recoil products formed in the uranium target reactions are deduced and show that the products in the₇₅Re to₈₃Bi region have backward peaked angular distributions characteristic of deep inelastic reactions. The heavy product angular distributions smoothly vary from a (1/sinθ) shape to an exponential shaped backward peak as the atomic number of the product increases from 52 to 83. The trend in the deduced angular distributions for those elements for which recoil range distributions were determined in the⁴⁰Ar+¹⁹⁷Au reaction and the 250 MeV⁴⁰Ar+²³⁸U reaction is similar, suggesting that just as for the Ar+Au system the composite system for the uranium target reaction is also not fully equilibrated along the mass asymmetry coordinate. These conclusions show that the fraction of the total reaction cross section resulting in complete fusion must be re-evaluated for the⁴⁰Ar+²³⁸U reaction and similar heavy-target reactions.     

Cs(6 ~2D_(5/2))与H_2反应生成的CsH分子的转动和振动态分布

利用激光泵浦-探测技术,在样品池条件下,研究了Cs(6D5/2)态与H2反应生成的CsH分子基电子态的转动和振动的量子态分布。在Cs-H2混合蒸气中,脉冲激光双光子激发Cs(6D5/2)态,另一台调频脉冲激光器扫描CsHX1Σ+(v″,J″)→A1Σ+(v′,J′=J″±1)吸收线,发现CsH分子只有v″=0和1上的振动带上有布居而不布居在v″1的振动带上。v″=0和1上的转动带分布呈现单峰结构,其峰值位于J″=6～8处,转动带分布轮廓与池温下的统计分布接近。转动Boltzmann温度分别为(458±20)K(对v″=1)和(447±18)K(对v″=0),得到的CsH分子的转动温度稍低于池温。从转动态分布得到v″=1与v″=0上布居数之比约为0.897,从而计算出CsH基电子态上的平均转动能ER和平均振动能EV,有效能减去平均振转能得到平均平动能ET。CsH分子3种能量的相对比值fT∶fV∶     

H2F2 chain reaction rate investigation

Experimental performance of chemical lasers pumped by the H₂ + F₂ chain reaction has consistently fallen below expectations, although the “hot”, H+F₂→HF(ν)+F, pumping reaction produces greater vibrational excitation than the “cold”, F+H₂→HF(ν)+H, reaction used in most HF cw chemical lasers. The reasons for this discrepancy are examined by measuring spatially-resolved HF(ν) number density and the temperature profiles in a laminar, parallel flow, hydrogen-fluorine mixing layer and comparing the results with theoretical computations. By dissociating either the hydrogen or fluorine molecules with arc heaters, kinetics of the hot and cold reaction systems are separately investigated. From a comparison of the experimental vibrational populations and the theoretical predictions, it is concluded that: (1) previously-used pumping and deactivation rates associated with the cold reaction are approximately correct, (2) the deactivation of high vibrational levels populated by the hot reaction is much faster than previously stated in Ref. (1), and (3) the inclusion of multiquantum HF(ν) V-T (or V-R) deactivation reactions, which sharply decreases the number density of the upper vibrational levels, greatly improves the agreement between theory and experiment.     

Laser-induced fluorescence of Pb2

Pb₂, which occurs in lead vapor, was studied by the technique of laser-induced fluorescence using single-mode Ar-laser excitation. The fluorescence observed could be classified into the F-X system. Ten progressions involving vibrational quantum numbers v′ = 0?9 and v″ = 0?22 were analyzed. Including collision-induced lines, rotational quantum numbers from J = 25 to J = 300 were observed. The vibrational constants and the numbering of the states had to be reassigned. For the first time rotational constants were determined for the Pb₂ molecule. The internuclear distances of ²⁰⁸Pb₂ in the F and X state are $\text{r = 3.079}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{<mtext>e</mtext>}}\text{= 2.930}\text{A}\text{?}$, respectively. Using the constants derived RKR potentials and Franck-Condon factors were calculated, which confirmed the vibrational assignments and constants.     

Ground state rotational spectrum of nitrogen trifluoride: The K = 3 splittings of NF3 and NF3

The ground state rotational spectrum of the ¹⁴NF₃ and ¹⁵NF₃ isotopic species of nitrogen fluoride has been observed in the ∼450-810 GHz frequency range. This investigation allowed us to improve the rotational parameters for both isotopologues. In particular, for the first time the K = 3 line splitting parameter and the sextic centrifugal distortion constants have been determined for ¹⁵NF₃.     

Effect of ro-vibrational excitation of NeH~+ on the stereodynamics for the reactions H+NeH~+(v=1-3,j=1,3,5) →H_2~++Ne

The stereodynamics of the abstraction reaction H + NeH+(v = 1-3,j = 1,3,5) → H2+ + Ne is studied theoretically with a quasi-classical trajectory method on a new ab initio potential energy surface [ S J,Zhang P Y,Han K L and He G Z 2012 J.Chem.Phys.132 014303].The effects of vibrational and rotational excitation of reagent molecules on the polarization of the product are investigated.The reaction cross sections,the distributions of P(θr),P(φr),and polarizationdependent differential cross sections(PDDCSs) are calculated.The obtained cross sections indicate that the title reaction is a typical barrierless atom(ion)-ion(molecule) reaction.The initial vibrational excitation and rotational excitation of reagent molecules have distinctly different influences on stereodynamics of the title reaction,and the possible reasons for the differences are presented.     

反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响

在Peterson的高精度从头计算势能面上,运用准经典轨线方法讨论了反应物分子初始振动激发对O+HCl→OH+Cl反应的立体动力学性质的影响.反映两矢量k-j′相关的P(θr)函数的分布说明产物的转动角动量j′在垂直于反应物相对速度矢量k的方向上的排列取向程度随着初始反应物振动量子数的增加而增加;反映三矢量k-k′-j′相关的极角分布函数P(r)显示产物的转动角动量有比较弱的定向效应,且随着初始振动量子数的增加,这种弱的定向效应由沿Y轴负向变为沿Y轴正向.说明反应物分子的初始振动激发有利于增强产物分子的转动排列取向效应,但对产物分子P(r)分布的影响则不明显.     

反应物振动激发对O(3P)+D2→OD+D立体动力学的影响

运用准经典轨线方法,基于Roger的³A"势能面,在碰撞能为104.5 kJ/mol时对O(³P)+D₂反应的立体动力学性质进行了理论研究. 详细讨论与产物矢量相关的的极化分布函数以及四个极化微分反应截面进行了. 结果表明,产物OD的立体动力学性质对反应物分子H_{2相似文献}   

Microwave spectrum of NF2

About 350 lines in the microwave spectrum of NF₂ have been measured in various ranges of frequency between 13.0 and 65.2 GHz by using two types of Zeeman effect spectrometers. Complete assignment of all lines has been achieved and, via the general microwave computer program SPINRO, the rotational constants, centrifugal distortion constants, dipole moment, electronic spin-rotation coupling constants, the constants for the coupling of the several nuclear spins with the electron spin and the nitrogen quadrupole coupling constants have all been obtained.By drawing upon the observed vibrational frequencies the average geometry of NF₂ has been evaluated. Force constants and Coriolis coupling constants have also been derived.The values of the spin coupling constants for N and for F indicate that NF₂ is a π-radical with the spin density mainly located on nitrogen. The multiplet patterns indicate that the ground electronic state wavefunction is antisymmetric to rotation about the molecular symmetry axis and so, for a π-radical, identifies the ground state as ²B₁ as has previously been assumed for this molecule.     

Diffractive production of vector mesons in lepton-nucleon reactions

We calculate cross sections for the production of vector mesons V in reactions if ? + N → ?' + V + N, ?, ?' = ν, e, μ, taking into account all presently known information from electroproduction of ?'s. This leads to considerable differences in results from previous calculations, often more than an order of magnitude. The results for the ? are then largely a translation of electroproduction data into ν predictions and they will provide a direct test of the relation of weak and electromagnetic currents. The y or Q² distributions for the ? are instructive. The prediction for the A₁ provides a direct test of the existence of the A₁ and of whether vector and axial vector currents materialize into particles in the same way. The detection of a B meson would provide direct evidence for second-class currents and a measurement of their strength. We estimate all F¹ production will account for at most 2% of the total ν cross section at FNAL energies, which must be multiplied by the muon semi-leptonic branching ratio (and possibly a factor of 2 for an axial vector F¹) to calculate its contribution to the dimuon event rate.     

O(1D)和CD4反应的准经典轨线

在新的全域势能面上, 用准经典轨线方法细致地研究了O(¹D)+CD₄多通道化学反应的动力学．这个势能面是用交换不变多项式方法基于MRC+Q/aug-cc-pVTZ从头算点拟合得到的．通过计算得到了产物OD+CD₃、D+CD₂OD/CD₃O和D₂+DCOD/D₂CO的分支比、平动能分布以及角度分布,结果显示理论与实验吻合得较好, 从而说明了这个反应的同位素取代效应很小． 研究表明,O(¹D)+CD₄反应是经过陷入的抽取机理发生的： 最初主要通过D原子的抽取,并不是之前人们认为的直接C-D键的插入形成CD3OD中间物后再进而解离成各个产物通道．     

The reaction of F atoms with CO in an argon matrix. Vibrational and electronic spectra of FCO

Upon codeposition at 14 K of an Ar:CO sample with an Ar:NF₃ sample that had been passed through a low-power microwave discharge in an Al₂O₃ tube, very prominent infrared absorptions of FCO and F₂CO were observed. Overtone bands of FCO were identified at 2032 and 3690 cm⁻¹, and their assignment was confirmed by both carbon-13 and oxygen-18 isotopic substitution. Further data were also obtained on the vibrational fundamentals of isotopically substituted F₂CO. A six-constant valence force potential has been derived for FCO using a least-squares force constant adjustment to the isotopic data and assuming a recently calculated structure. The photodissociation of FCO into F + CO was observed with a threshold near 2800 Å. The assignment of two overlapping electronic transitions of FCO between 3400 and 2300 Å is discussed.     

225∽260 nm波段溴化氰光解动力学系统性研究

本文报道了在自行搭建的时间切片离子速度成像装置上进行的225∽260 nm波段内溴化氰光解动力学的研究. 在该波段内选取了若干溴原子(²P_3/2或²P_1/2)的共振线对产物溴原子的共振电离并采集其切片影像,得到了光解产物的总平动能谱,进而获得了产物氰基的振转态布居等信息. 本文发现了在Br^*通道,产物氰基的内能激发比Br通道低;Br和Br^*通道产物氰基振动的最高布居分别为v=0和1. 另外,还发现对于Br通道,溴化氰分子在长波处与短波处解离时,氰基产物的振转激发差异很大,这揭示了其显著不同的光解动力学.     

Semiclassical and quasiclassical calculation of reaction probabilities for collinear X + F2→XF + F (X = Mu,H, D,T)

Semiclassical calculations of reaction probabilities have been carried out for the collinear H + F₂ (n = 0, 1) reaction using the best extended LEPS surface No. II of Jonathan et al. Both real and complex valued classical trajectories have been included in the calculations for an energy range where the quasiclassical total reaction probability is unity. Comparison with quantum results shows the semiclassical reaction probabilities are accurate to about ± 0·05 provided only two real or complex stationary phase points make an important contribution to the S matrix element, so that the uniform Airy or integer Bessel approximations are valid. Real semiclassical calculations are also reported for the collinear Mu, D, T + F₂ (n = 0) reactions. For the D and T reactions, the semiclassical reaction probabilities are estimated to be accurate to ± 0·05, except close to the reaction threshold, but for the Mu reaction the estimated errors are much larger. In addition, quasiclassical calculations for the reaction probabilities have been carried out using half integer boxing and smooth sampling methods to quantize the product distributions. For the H + F₂ reaction, there are usually systematic deviations from the quantum reaction probabilities and the same is expected to be true for the Mu, D and T reactions.     

Vibrational,rotational, and isotopic dependence of CaBr X2Σ spin-rotational and HFS parameters

The previously published molecular-beam, laser-rf, double-resonance study of the rotational and isotopic dependences of the spin-rotational and hyperfine interactions in the v″ = 0, X²Σ state of CaBr is supplemented here with data for v″ = 1. The vibrational dependence of the parameters is now obtained. The results for CaBr are displayed along with analogous, previously published results for CaF and CaCl.     

X-ray emission and X-ray photoelectron spectroscopic studies of fullerene fluoride C<Subscript>60</Subscript>F<Subscript>24</Subscript>

The structure of the fullerence fluoride C₆₀F₂₄ of the T _h symmetry contains two types of chemically different carbon atoms, namely, atoms of isolated double bonds and atoms of CF groups. X-ray photoelectron and x-ray emission spectroscopic studies of C₆₀F₂₄ revealed a difference in the widths of the x-ray bands corresponding to these types of atoms. Nonempirical quantum-chemical calculations performed for C₅₉NF ₂₄ ⁺ ions with a hole in the C 1s core level of the fullerence fluoride showed that the difference in the bandwidths may be due to the fact that the vibrational states of the system are different when 1s electrons are removed from chemically nonequivalent atoms.     

O+DC1→OD+Cl反应在~3 A″势能面上的动力学研究(英文)

在~3A″势能面上,在散射能为14～20 kcal/mol的范围内,运用准经典轨线方法对O+DCl→OD+Cl进行了动力学研究.我们发现积分散射截面随着散射能的增加而增大,产物OD的振动分布发生了很强的粒子数的反转现象,且振动激发较弱、转动激发较强.后向散射居于主导地位,碰撞能的变化对产物转动取向的影响不大.     

Angle-resolved desorption and removal of surface nitrogen in deNOx

This paper reports on recent progress on angle-resolved desorption leading to structure-sensitive desorption dynamics. The sensitivity is exemplified in NO and N₂O reduction on Pd and Rh surfaces. The energy partitioning in the repulsive desorption of hyper-thermal products into their rotational and translational modes is an indispensable concept to examine the structure of a reaction site from desorbing molecules because it connects the structure of a transition state with each energy of desorbed products. The extent of the energy partitioning will be derived from the desorption-angle dependences of both the rotational and translational energies at each vibrational state. Such energy analysis has never been completed for any thermal reactive desorption. A new type of measurement is thus proposed. Additionally, we discuss the inadequate use of the detailed balance principle in desorption dynamics, which has prevented desorption dynamics from being sensitive to surface structures.     

Reactive scattering of a supersonic deuterium atom beam : D+Br2, CF3I,C2F5I,C3F7I

Reactive scattering of D atoms with Br₂, CF₃I, C₂F₅I and C₃F₇I molecules has been studied at an initial translational energy E = 5·3 kJ mol^-1 using a supersonic beam of D atoms seeded in He. Deuterium halide product is scattered in the backward direction with respect to the incident D atoms, with substantial energy disposed into product translation in all cases. The fraction of the total available energy which is disposed into product translation, is greater for the fluoralkyl iodides than for Br₂ and decreases slightly along the series CF₃I, C₂F₅I, C₃F₇I. These results demonstrate that the reaction of D atoms with fluoroalkyl iodides occurs only in collisions at small impact parameters with strong repulsion between the reaction products. The potential energy surfaces for the reactions of the fluoroalkyl iodides are similar to that for the D + Br₂ reaction but involve the release of a still greater proportion of the reaction exoergicity in the exit valley of the surface. Only a small fraction, if any, of the product repulsion is transferred to internal excitation of the product fluoroalkyl radical.