离子对生成反应截面的量子散射理论研究

将Miller的S-矩阵变分法推广到离子对生成反应动力学的研究。M＋X~2→M^+＋X~2^-反应体系包括共价态(M＋X~2)和离子态(M^+＋X~2^-)两个势能面及其交叉效应,本文在此两态模型下导出了生成截面公式。在矩阵元计算中,平动波函数采用分布Gauss基作展开。作为上述公式的应用,对Cs＋O~2→Cs^+＋O~2^-反应体系作了数值计算并取得了满意结果。     

Schematic model for the differential cross section in ion-pair formation

An analytic approximation to the differential cross section is derived for ion-pair formation in a model two-state (“turned-on Coulomb”) system. The result gives insight into the structure observed in recent experiments.     

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.     

The influence of the rate of bond stretching on the differential cross sections for ion-pair formation in K + XY collisions

Experimental differential cross sections are presented for ion-pair formation in collisions between K and I₂, IBr, Br₂, ICl, Cl₂. In this sequence the vibrational frequency of the halogen molecule is increased gradually from one system to the next. Therefore this is a suitable set of cros sections for analysing the influence of the rate at which the halogen bond stretches after transition to the ionic state. The experimental data are compared with trajectory calculations on diabatic and on adiabatic potential energy surfaces. The results of the two types of calculations differ significantly; the adiabatic model gives the better agreement with experiment. The essential difference between the two models is that in the diabatic model stretching of the halogen bond starts only when the crossing seam R_c between the ionic and covalent configurations is reached, while in adiabatic scattering, pre-stretching of the halogen bond occurs as the alkali atom approaches the crossing seam. As a result of pre-stretching the electron affinity is increased, which in turn affects the endoergicity and the total and differential cross sections for ion-pair formation. At energie below the threshold for ion-pair formation, the cross section for reactive scattering is also affected.     

Absolute electron-impact total ionization cross sections of chlorofluoromethanes

An experimental study is reported on the electron-impact total ionization cross sections (TICSs) of CCl4, CCl3F, CCl2F2, and CClF3 molecules. The kinetic energy of the colliding electrons was in the 10-85 eV range. TICSs were obtained as the sum of the partial ionization cross sections of all fragment ions, measured and identified in a linear double focusing time-of-flight mass spectrometer. The resulting TICS profiles--as a function of the electron-impact energy--have been compared both with those computed by ab initio and (semi)empirical methods and with the available experimental data. The computational methods used include the binary-encounter-Bethe (BEB) modified to include atoms with principal quantum numbers n> or =3, the Deutsch and M?rk (DM) formalism, and the modified additivity rule (MAR). It is concluded that both modified BEB and DM methods fit the experimental TICS for (CF4), CClF3, CCl2F2, CCl3F, and CCl4 to a high accuracy, in contrast with the poor accord of the MAR method. A discussion on the factors influencing the discrepancies of the fittings is presented.     

Nonadiabatic collision model calculations of ion-pair formation cross sections of Cs+O2→Cs++O

This paper has improved Hickman's nonadiabatic collision model by substituting Hickman's constant velocity classical straight line trajectory approximation with the solution of motion equation mR=?dV(R)/dR, and has calculated the cross sections of ion-pair formation Cs+O₂→Cs⁺+O^?₂ with the improved nonadiabatic collision model (INCM). A comparison of our results with other theoretical and experimental results has been made.     

Angle dependent total cross sections and the optical theorem

Cross sections are either represented by generalized asymptotical partial wave expansions or obtained as a spherical average of an appropriate differential cross section. In these cases it is usually assumed that the total scattering cross section, as a property of a scattering object, does not depend on the incident angles. This viewpoint is supported by common knowledge in connection with low energy scattering. However this unconscious belief is not always correct. In the present paper we will show that a non-spherical scatterer may exhibit strong dependence on the incident direction. To do this we will represent the scattering data of the most general potential, separable in ellipsoidal coordinates, in perturbed ellipsoidal (Lamé) wave functions. These functions arise when variables in the Schr?dinger equation are separated in an ellipsoidal coordinate system. The Lamé wave functions are analogous to spherical- and Bessel functions in the case of spherical symmetry. We will expand the total scattering cross section and derive the optical theorem explicitly demonstrating the incident angle dependence for such a class of potentials. As an illustration we will present and display some calculations of the total cross section versus incident direction. Unexpected behavior will be discussed and explained. We also use results from classical acoustic scattering by a triaxial ellipsoid. The general character of the ellipsoidal coordinate system is emphasized.     

Measurements of total cross sections for electron scattering from helium and argon

A time-of-flight (TOF) electron spectrometer has been used to measure absolute total cross sections (TCS) scattered from helium and argon over the energy range from 1 to 50 eV. The TOF spectrometer and experimental procedure are described briefly, and experimental results are presented together with associated errors. The results are found to be in good agreement with other experimental and theoretical data.     

On the estimation of cross sections for the formation of triatomic collision complexes

The traditional procedure of associating the formation of a collision complex with the passage over a centrifugal potential barrier is reinvestigated. It is argued that the complex is better defined in terms of a spatially localized critical surface (or separation), such that the complex is strongly coupled, while the system is weakly elsewhere. Weak coupling implies that the rotational and vibrational energies of the diatomic fragment are, to a good approximation, conserved. Strong coupling implies that only total energy and angular momentum is conserved. Graphical methods are used to obtain upper bounds for the cross section within weak or strong coupling dynamics by optimizing the attraction within the given constraints. Results for a K + NaCl system and a O(¹D)+H₂ system are presented and compared with results of molecular dynamic simulations available in the literature. The weak coupling constraints are found to give a useful representation of the simulation data. Discontinuities in the optimal orientation of approach indicate the presence of orientational barriers.     

Collision cross sections for protein ions

A method for the determination of cross sections for gas-phase protein ions, based on the energy loss of ions as they pass through a collision gas, is described. A simple model relates the energy loss to the number of collisions and hence the cross section. Results from a Monte Carlo model that support the validity of this approach are described. Experimental cross sections are reported for motilin, ubiquitin, cytochrome c, myoglobm, and bovine serum albumin. Cross sections range from approximately 800 Ų for motilin to approximately 14,000 Ų for bovine serum albumin and generally increase with the number of charges on the ion. Cytochrome c ions from aqueous solution show somewhat smaller cross sections than ions formed from solutions of higher organic content, suggesting that the gas-phase ions may retain some memory of their solution conformation.     

Random-phase approximation for transport cross sections

The random-phase approximation is tested for the first two transport cross sections with several potential functions. Fairly good results are obtained, and the approximation is recommended for exploratory calculations, since it requires very little computational effort.     

Absolute total cross sections for scattering of hydrogen atoms by argon,krypton and xenon

Absolute total cross sections for scattering of hydrogen atoms by argon, krypton and xenon were measured as a function of velocity in the range from 1.8 to 6.2 km/sec. An analysis in terms of Lennard-Jones (12.6) and (8.6) model potentials leads to estimates of the interatomic forces.     

Differential, partial and total electron impact ionization cross sections for SF(6)

Single and double differential ionization cross sections for the production of ions resulting from dissociative, single and double ionization of SF(6) by electron impact have been calculated using a semiempirical formulation based on the Jain-Khare approach. In addition, triple differential cross sections have been obtained for some of the doubly charged fragment ions at an incident electron energy of 100, 150, and 200 eV, respectively, and a fixed scattering angle of 30 degrees. As no previous data seem to exist for differential cross sections we have derived from these differential cross sections corresponding partial and total ionization cross sections from threshold up to 900 eV and compared those with the available theoretical and experimental data.     

Comparison of measured total integral cross sections for noble gas dimer-atom systems with IOSA calculations

Experimentally determined total integral cross sections for noble gas dimer-atom systems, involving the energetically accessible channels of excitation, exchange and dissociation are compared with theoretical values calculated using a simple formula. This simple formula is derived using the multichannel optical theorem and the infinite order sudden approximation (IOSA). The potential is well approximated by the sum of known pair potentials. Setting the IOSA parameters L and K equal to the angular momentum and the wave number of the initial channel, respectively, the largest error between the experimental and theoretical results is about 10%. We noticed that a proper choice of the relation between K and the collision energy greatly reduces this error; a possible explanation cannot be given.     

Activation cross sections for the element rhenium

The¹⁸⁵Re(n,)¹⁸²Ta,¹⁸⁷Re(n,)¹⁸⁴Ta,¹⁸⁷Re(n,p)¹⁸⁷W and¹⁸⁷Re(n,2n)^186gRe reaction cross sections included by 13.5–14.7 MeV neutrons were measured by the activition method. The neutron fluences were determined by the cross section of the²⁷Al(n,)²⁴Na reaction. The neutron energies in these measurements were determined by the cross section ratios for⁹⁰Zr(n,2n)^89m+gZr and⁹³Nb(n,2n)^92mNb reactions.     

Calculation of cross sections for positron-Ar collisions

The three-body classical trajectory Monte-Carlo (CTMC) method is used to investigate positron-argon atom collisions. The total ionization cross sections are presented along with singly and doubly differential cross sections. The existence of the cusp-like peak in the triply differential electron and positron spectra at positron impact is predicted.     

Removal cross sections for 14.6 MeV neutrons

This paper reports on the determination of removal cross sections for different materials as paraffin, lead, graphite, concrete, and wood. The experimentally determined values of removal cross sections concerning these materials are respectively: 0.072±0.001, 0.089±0.003, 0.067±0.006, 0.071±0.003 and 0.0360±0.0005 cm^–1.     

Multiple ionization effects on total L-shell X-ray production cross sections by proton impact

The effect of multiple ionization on total L-shell X-ray production cross sections by proton impact, with energies below 1 MeV, on elements with atomic numbers in the range 26–55 was studied. Measurements of those cross sections for several elements were also done to enlarge the experimental database. Several tables for atomic parameters (fluorescence yields and Coster–Kronig transition probabilities) were used. The agreement between theory and experiment was optimized when average fluorescence yields given by Hubbel et al. (J. Phys. Chem. Ref. Data 23(2) (1994) 339) and a multiple ionization model proposed by Lapicki et al. (Phys. Rev. A 34(5) (1986) 5813) were used together. Thus, improvements to theoretical predictions for ionization cross sections should consider first a correct set of atomic parameters.     

The determination of absolute anion formation cross sections from electron beam scattering data

Using recent low energy electron scattering data for CCl4 and SF6, and accompanying theory illustrating the coupling of attachment and elastic scattering, absolute cross sections are derived for electron attachment to CCl4 and SF6 between impact energies, respectively, of 8-52 meV and 7-42 meV. Values of attachment cross sections are compared with those obtained by laser and threshold photoionization techniques, which include normalization to rate coefficient data. Excellent agreement with the latest CCl4 data is obtained, with less precise agreement for SF6, but still lying within experimental uncertainties.