非相对论重离子碰撞动力学的两体关联输运理论

论文系统地介绍和分析了当前几类描述重离子碰撞动力学过程输运理论的优点和缺点，并针对这些理论的不足作为建立我们理论模型的出发点。例如BUU（Boltzmann-Uehling-Uhlenbeck）系列的输运过程，可以通过不同方法从量子多体理论依照扩展的时间相关的Hartree-Fock（ETDHF）的基本思想推导出来，并对重离子碰撞过程中有关平均场物理量给出了合理的描述。但由于推导中采用了一些半经典近似和参数化近似，破坏了平均场合碰撞项之间的动力学自洽耦合。特别是数值计算中采用了实验粒子系综平均法，从而丢失了多体关联和涨落，使其无法直接描述重离子碰撞中基本的碎块形成和多重碎裂过程。而量子分子动力学（QMD）系列的理论能够给出重离子碰撞过程中碎块形成的动力学描述，但至今无法从量子多体理论推导出有关QMD的输运方程。碰撞项是在数值计算中通过Monte Carlo抽样技术人为地加入的。那么，如何从量子多体理论出发推导出描述重离子碰撞动力学过程的，可将时间相关的平均场，多体关联进行自洽耦合描述的量子输运理论就成了本论文工作的中心目的。 基于王顺金等人建立的多体关联动力学理论，选用时间相关的相干态单粒子基矢作为新理论的工作表象，对两体关联动力学中的一体密度矩阵和两体关联函数进行轨道展开，推导出了描述非相对论重离子碰撞动力学过程的两体关联输运理论TBCTT（Two-Body Correlation Transport Theory）。TBCTT是一组包括时间相关的平均场，两体关联和Pauli原理的自洽耦合的动力学方程组。其中时间相关的相干单粒子基矢是该理论的一个关键问题。其时间演化的动力学可由多种不同的方法得到，如时间相关的Hartree-Fock方法，时间相关的变分方法等。但作为建立TBCTT工作的第一步，为了计算简便，我们采用经典的Hamilton方程来描述相干单粒子基矢中相空间参数的时间演化，然后通过与两体关联动力学的耦合而恢复TBCCT基本的量子特征。 利用TBCTT对几组轻的碰撞系统进行了数值计算和分析。计算结果表明：TBCTT可以给出重离子碰撞过程中的有关物理量时间演化过程的合理描述，得到了在不同入射道条件下与QMD模型的可比性结果。同时也在组态空间的有限截断和两体关联函数不同的等级截断下均得到了碰撞系统总动量，总能量和总粒子数的近似守恒结果，特别是能量守恒，这是一般半经典输运理论中一个重要的困难问题。另外还得到了两体关联函数不同的等级截断近似对碰撞动力学方面不同的描述。所用这些数值计算结果充分表明：TBCTT是一个有希望和有发展前途的能够描述重离子碰撞动力学的量子输运理论。最后我们对当前计算中所采用的近似和存在的问题进行了分析和讨论，提出了进一步改进和完善TBCTT的途径和方案。 我们在开始TBCTT的研究之前还对QMD进行了仔细的研究和改进。通过在平均场中引入Pauli势和对称势并利用摩擦冷却方法构造原子核基态，得到了一种改进的量子分子动力学MQMD。利用这种MQMD研究了12C+12C反应多重碎裂过程中的核结构效应，得到了与AMD和实验数据基本一致的结果。对QMD的改进和应用为开展TBCTT的研究工作创造了必要条件和准备。

SOLVENT AND SUBSTITUENT EFFECTS ON THE INTRAMOLECULAR AMIDE HYDROLYSIS OF N-METHYLMALEAMIC ACID

Intramolecular amide hydrolysis of N-methylmaleamic acid is revisited at the B3LYP/6-311G(2df,p)//B3LYP/6-31G(d,p)+ZVPE level, including solvent effects at the CPCM-B3LYP/6-311G(2df,p)//Onsager-B3LYP/6-31G(d,p)+ZPVE level. The concerted reaction mechanism is energetically favorable over stepwise reaction mechanisms in both the gas phase and solution. The calculated reaction barriers are significantly lower in solution than in the gas phase. In addition, it is concluded that the substituents of the four N-methylmaleamic acid derivatives considered herein have a significant effect on the gas-phase reaction barriers but a smaller, or little, effect on the barriers in solution.

Structural stability and electronic state of transition metal trimers

Ground state geometries were searched for transition metal trimers Sc-3, Y-3, La-3, Lu-3, Ti-3, Zr-3, and Hf-3 by density functional methods. For all the studied trimers, our calculation indicates that the ground state geometries are either equilateral triangle (Zr-3 and Hf-3) or near equilateral triangle (Ti-3, Sc-3, Y-3, La-3, and Lu-3). For rare earth trimers Sc-3, Y-3, La-3, and Lu-3, isosceles triangle (near equilateral triangle) at quartet state is the ground state. Isosceles triangle at doublet state is the competitive candidate for the ground state. For Zr-3 and Hf-3, equilateral triangle at singlet state is the most stable. For Ti-3, isosceles triangle (near equilateral triangle) at quintet state gives the ground state. For Sc-3, Zr-3, and Hf-3, where experimental results are available, the predicted geometries are in agreement with experiment in which the ground state is equilateral triangle (Zr-3) or fluxional (Sc-3 and Hf-3). For Y-3, the calculated geometry is in agreement with experimental observation and previous theoretical study that Y-3 is a bent molecule for the ground state.

Gas-phase ion-molecule reactions of C-60 and theoretical studies of [C60C2H3O](+) adduct cations

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the acetyl cation CH3-C-+=O (m/z 43) and formylmethyl cation (CH2)-C-+-CH=O (m/z 43, or oxiranyl cation), generated from the self-chemical ionization of acetone and vinyl acetate, respectively, were studied in the ion source of a mass spectrometer. Adduct cations [C60C2H3O](+) (m/z 763) and protonated C-60, [C60H](+) (m/z 721), were observed as the major products. AM1 semiempirical molecular orbital calculations on the possible structures, stabilities and charge locations of the isomers of the adducts [C60C2H3O](+) were carried out at the restricted Hartree-Fock level. The results indicated that the sigma-addition product [C-60-COCH3](+) is the most stable adduct for the reaction of C-60 with CH3-C-+=O rather than that resulting from the [2+2] cycloaddition. The [2+3] cycloadduct and the sigma-adduct [C60CH2CHO](+) might be the most possible coexisting products for the reactions of C-60 with (CH2)-C-+-CH=O or oxiranyl cation. Other [C60C2H3O](+) isomers are also discussed. (C) 1997 by John Wiley & Sons, Ltd.

基于三坐标测量机激光拼焊板材直线度研究

利用高精度三坐标测量机扫描功能,充分获得焊接板材端面线性三维数据坐标值,采用基于最小二乘法而建立的理想直线数学模型来评定直线度误差,并与实际采用塞尺法进行对比,结果发现采用三坐标测量更能详尽地反应整个焊接边缘直线度真实情况,节省大量的数据处理时间,且数据更加准确可靠,并在实际激光焊接中获得良好激光焊缝,同时直观地给出了焊接板材边缘线性特征,为剪板机刀具调整提供了方向与位置。

Properties of molecules in tunnel junctions

Molecular tunnel junctions involve studying the behaviour of a single molecule sandwiched between metal leads. When a molecule makes contact with electrodes, it becomes open to the environment which can heavily influence its properties, such as electronegativity and electron transport. While the most common computational approaches remain to be single particle approximations, in this thesis it is shown that a more explicit treatment of electron interactions can be required. By studying an open atomic chain junction, it is found that including electron correlations corrects the strong lead-molecule interaction seen by the ΔSCF approximation, and has an impact on junction I − V properties. The need for an accurate description of electronegativity is highlighted by studying a correlated model of hexatriene-di-thiol with a systematically varied correlation parameter and comparing the results to various electronic structure treatments. The results indicating an overestimation of the band gap and underestimation of charge transfer in the Hartree-Fock regime is equivalent to not treating electron-electron correlations. While in the opposite limit, over-compensating for electron-electron interaction leads to underestimated band gap and too high an electron current as seen in DFT/LDA treatment. It is emphasised in this thesis that correcting electronegativity is equivalent to maximising the overlap of the approximate density matrix to the exact reduced density matrix found at the exact many-body solution. In this work, the complex absorbing potential (CAP) formalism which allows for the inclusion metal electrodes into explicit wavefunction many-body formalisms is further developed. The CAP methodology is applied to study the electron state lifetimes and shifts as the junction is made open.

Accurate localized resolution of identity approach for linear-scaling hybrid density functionals and for many-body perturbation theory

© 2015 IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.A key component in calculations of exchange and correlation energies is the Coulomb operator, which requires the evaluation of two-electron integrals. For localized basis sets, these four-center integrals are most efficiently evaluated with the resolution of identity (RI) technique, which expands basis-function products in an auxiliary basis. In this work we show the practical applicability of a localized RI-variant ('RI-LVL'), which expands products of basis functions only in the subset of those auxiliary basis functions which are located at the same atoms as the basis functions. We demonstrate the accuracy of RI-LVL for Hartree-Fock calculations, for the PBE0 hybrid density functional, as well as for RPA and MP2 perturbation theory. Molecular test sets used include the S22 set of weakly interacting molecules, the G3 test set, as well as the G2-1 and BH76 test sets, and heavy elements including titanium dioxide, copper and gold clusters. Our RI-LVL implementation paves the way for linear-scaling RI-based hybrid functional calculations for large systems and for all-electron many-body perturbation theory with significantly reduced computational and memory cost.

Role of Landau quantization on the neutron-drip transition in magnetar crusts

The role of a strong magnetic field on the neutron-drip transition in the crust of a magnetar is studied. The composition of the crust and the neutron-drip threshold are determined numerically for different magnetic field strengths using the experimental atomic mass measurements from the 2012 Atomic Mass Evaluation complemented with theoretical masses calculated from the Brussels-Montreal Hartree-Fock-Bogoliubov nuclear mass model HFB-24. The equilibrium nucleus at the neutron-drip point is found to be independent of the magnetic field strength. As demonstrated analytically, the neutron-drip density and pressure increase almost linearly with the magnetic field strength in the strongly quantizing regime for which electrons lie in the lowest Landau level. For weaker magnetic fields, the neutron-drip density exhibits typical quantum oscillations. In this case, the neutron-drip density can be either increased by about 14% or decreased by 25% depending on the magnetic field strength. These variations are shown to be almost universal, independently of the nuclear mass model employed. These results may have important implications for the physical interpretation of timing irregularities and quasiperiodic oscillations detected in soft gamma-ray repeaters and anomalous x-ray pulsars, as well as for the cooling of strongly magnetized neutron stars.

Energy levels and transition probabilities for nitrogen-like Fe xx

Energies of the 700 lowest levels in Fe XX have been obtained using the multiconfiguration Dirac-Fock method. Configuration interaction method on the basis set of transformed radial orbitals with variable parameters taking into account relativistic corrections in the Breit-Pauli approximation was used to crosscheck our presented results. Transition probabilities, oscillator and line strengths are presented for electric dipole (E1), electric quadrupole (E2) and magnetic dipole (M1) transitions among these levels. The total radiative transition probabilities from each level are also provided. Results are compared with data compiled by NIST and with other theoretical work.

Ionization energies of beryllium in strong magnetic fields: a frozen core approximation

An effective frozen core approximation has been developed and applied to the calculation of energy levels and ionization energies of the beryllium atom in magnetic field strengths up to 2.35 x 10(5) T. Systematic improvement over the existing results for the beryllium ground and low-lying states has been accomplished by taking into account most of the correlation effects in the four-electron system. To our knowledge, this is the first calculation of the electronic properties of the beryllium atom in a strong magnetic field carried out using a configuration interaction approximation and thus allowing a treatment beyond that of Hartree-Fock. Differing roles played by strong magnetic fields in intrashell correlation within different states are observed. In addition, possible ways to gain further improvement in the energies of the states of interest are proposed and discussed briefly.

Independent particle descriptions of tunneling using the many-body quantum transport approach

Currents across thin insulators are commonly taken as single electrons moving across classically forbidden regions; this independent particle picture is well-known to describe most tunneling phenomena. Examining quantum transport from a different perspective, i.e., by explicit treatment of electron-electron interactions, we evaluate different single particle approximations with specific application to tunneling in metal-molecule-metal junctions. We find maximizing the overlap of a Slater determinant composed of single-particle states to the many-body current-carrying state is more important than energy minimization for defining single-particle approximations in a system with open boundary conditions. Thus the most suitable single particle effective potential is not one commonly in use by electronic structure methods, such as the Hartree-Fock or Kohn-Sham approximations.

Correlated electron-ion dynamics: the excitation of atomic motion by energetic electrons

Correlated electron-ion dynamics (CEID) is an extension of molecular dynamics that allows us to introduce in a correct manner the exchange of energy between electrons and ions. The formalism is based on a systematic approximation: small amplitude moment expansion. This formalism is extended here to include the explicit quantum spread of the ions and a generalization of the Hartree-Fock approximation for incoherent sums of Slater determinants. We demonstrate that the resultant dynamical equations reproduce analytically the selection rules for inelastic electron-phonon scattering from perturbation theory, which control the mutually driven excitations of the two interacting subsystems. We then use CEID to make direct numerical simulations of inelastic current-voltage spectroscopy in atomic wires, and to exhibit the crossover from ionic cooling to heating as a function of the relative degree of excitation of the electronic and ionic subsystems.

Absolute photoionization cross sections for Xe4+, Xe5+, and Xe6+ near 13.5 nm: Experiment and theory

Absolute photoionization cross-section measurements for a mixture of ground and metastable states of Xe4+, Xe5+, and Xe6+ are reported in the photon energy range of 4d -> nf transitions, which occur within or adjacent to the 13.5 nm window for extreme ultraviolet lithography light source development. The reported values allow the quantification of opacity effects in xenon plasmas due to these 4d -> nf autoionizing states. The oscillator strengths for the 4d -> 4f and 4d -> 5f transitions in Xeq+ (q=1-6) ions are calculated using nonrelativistic Hartree-Fock and random phase approximations. These are compared with published experimental values for Xe+ to Xe3+ and with the values obtained from the present experimental cross-section measurements for Xe4+ to Xe6+. The calculations assisted in the determination of the metastable content in the ion beams for Xe5+ and Xe6+. The experiments were performed by merging a synchrotron photon beam generated by an undulator beamline of the Advanced Light Source with an ion beam produced by an electron cyclotron resonance ion source.

Configuration-interaction effects in and intensity dependence of F- multiphoton detachment

Two- and three-photon detachment rates have been obtained for F- using several expansions in the R-matrix Floquet approach. These rates are compared with other theoretical and experimental results. The use of Hartree-Fock wavefunctions for the ground state of F with addition of continuum electrons does not lead to agreement with experiment for two- and three-photon detachment. By adding correlation terms, agreement with experiment and other theoretical results is improved considerably, demonstrating the importance of electron correlation effects. However, convergence with respect to the wavefunction expansion cannot be established, we also study the intensity dependence of multiphoton detachment rates for F- at the Nd-YAG frequency. Due to the ponderomotive shift the three-photon detachment channel closes at an intensity of 8.5 x 10(11) W cm(-2) and the influence of this channel closure on the multiphoton detachment peaks is illustrated by determining the heights of the excess-photon peaks obtained using a Gaussian laser pulse.

Exchange potential from the common energy denominator approximation for the Kohn-Sham Green's function: Application to (hyper)polarizabilities of molecular chains

An approximate Kohn-Sham (KS) exchange potential v(xsigma)(CEDA) is developed, based on the common energy denominator approximation (CEDA) for the static orbital Green's function, which preserves the essential structure of the density response function. v(xsigma)(CEDA) is an explicit functional of the occupied KS orbitals, which has the Slater v(Ssigma) and response v(respsigma)(CEDA) potentials as its components. The latter exhibits the characteristic step structure with "diagonal" contributions from the orbital densities \psi(isigma)\(2), as well as "off-diagonal" ones from the occupied-occupied orbital products psi(isigma)psi(j(not equal1)sigma). Comparison of the results of atomic and molecular ground-state CEDA calculations with those of the Krieger-Li-Iafrate (KLI), exact exchange (EXX), and Hartree-Fock (HF) methods show, that both KLI and CEDA potentials can be considered as very good analytical "closure approximations" to the exact KS exchange potential. The total CEDA and KLI energies nearly coincide with the EXX ones and the corresponding orbital energies epsilon(isigma) are rather close to each other for the light atoms and small molecules considered. The CEDA, KLI, EXX-epsilon(isigma) values provide the qualitatively correct order of ionizations and they give an estimate of VIPs comparable to that of the HF Koopmans' theorem. However, the additional off-diagonal orbital structure of v(xsigma)(CEDA) appears to be essential for the calculated response properties of molecular chains. KLI already considerably improves the calculated (hyper)polarizabilities of the prototype hydrogen chains H-n over local density approximation (LDA) and standard generalized gradient approximations (GGAs), while the CEDA results are definitely an improvement over the KLI ones. The reasons of this success are the specific orbital structures of the CEDA and KLI response potentials, which produce in an external field an ultranonlocal field-counteracting exchange potential. (C) 2002 American Institute of Physics.