Ab initio calculation of electronic transition moments for singlet excited states of the H2 molecule

Ab initio CI electronic dipole transition moments have been calculated for the transitions between singlet states of the hydrogen molecule correlating asymptotically with H(nl)+H(1s) (n=1,2,3). The investigated singlet-singlet transitions include the 30 (n=3) inter-Rydberg transitions and the 32 transitions which may contribute to absorption in the far wings of the Balmer α line of atomic hydrogen perturbed by another hydrogen atom in its ground state. Results are presented for internuclear distances 1.0a₀?R?12a₀. The present results compare well with the previous theoretical calculations available for about half of the transitions treated in the present work. Thirty eight new transitions are presented. Adiabatic potential energies for the and and improved energies for the and states are reported as well.     

Ab initio calculation of the dipole moment of cyanamide

The He(I) photoelectron spectra of the isoelectronic series Fe(CO)₂(NO)₂, Co(CO)₃NO and Ni(CO)₄ are reported and interpreted by means of ab initio SCF-MO calculations. For the nitrosyl complexes it is found that ionization potentials calculated assuming Koopmans' theorem are seriously in error due to the considerably greater orbital relaxation accompanying ionization from metal than from NO valence orbitals. When such allowance is made for orbital relaxation by performing restricted Hartree-Fock (RHF) calculations on the ionic states, the experimental spectra are accurately reproduced and the observed similarity of the spectra of all three molecules is explained.     

钫原子磁偶极超精细结构常数及其同位素的磁偶极矩的理论计算

应用基于B样条基组的相对论耦合簇理论方法,计算了~(212)Fr原子的n S (n=7—12), n P (n=7—12)和n D (n=6—11)态的磁偶极超精细结构常数.与精确实验值的比较说明这套理论方法能精确计算出磁偶极超精细结构常数,其中7P态的磁偶极超精细常数的理论值与实验值之间的差异小于1%.在忽略场移效应对Fr原子7P态超精细结构常数的影响下,通过结合实验值进一步定出了~(207-213,220-228)Fr核磁偶极矩μ,这些值与已有的测量值具有非常好的一致性.本文报道了12S, n P (n=9—12)和n D (n=10—11)态的磁偶极超精细结构常数.     

Ab initio calculation of the superconducting transition temperature

The superconducting transition temperature is calculated for a series of representative metals from a selfconsistent LMTO-bandstructure calculation. We carefully avoid any uncontrolled approximations apart from the use of a local exchange-correlation potential and the rigid-ion approximation for the electron-phonon interaction, Our results for V, Nb, Ta, Mo, W, Pd, Pt, Pb clearly indicate that these popular approximations are incapable of reproducing the observed transition temperatures.     

TiN多型体高压相变的第一性原理计算

基于密度泛函理论框架下的赝势平面波方法,计算了B1(氯化钠结构)、B2(氯化铯结构)、B3(闪锌矿结构)、B_k(六方氮化硼结构)、B_h(碳化钨结构)和B8₁(砷化镍结构)6种TiN多型体的晶体结构、体积弹性模量和相对稳定性.计算指出,不存在B4(纤锌矿)结构的TiN.通过不同外压下的晶格弛豫得到每种结构的焓,发现外压 关键词： 氮化钛 赝势 高压相变 密度泛函理论     

Ab initio calculation of force constants and equilibrium geometries in polyatomic molecules

The force constants and equilibrium geometry of water were calculated ab initio from Hartree-Fock self-consistent field wavefunctions using the force method, and a 53/31, a 73/3 + 1 and a 95/41 + 2 gaussian lobe basis set. The force method proved to be very economic and numerically accurate.

The calculated values agree well with the experimental ones. Especially good is the agreement for the interaction constant F_rα . Calculated force constants for the 95/41 + 2 basis are: F_r = 9·158 mdyn/å, F_α = 0·8513 mdyn/å, F_rα = +0·3007, F_rr = -0·1724; the experimental values from isotope frequencies are: F_r = 8·456, F_α = 0·762, F_rα = +0·246, F_rr = -0·100 mdyn/å. The agreement in the geometry is also good for the 95/41 + 2 basis r _e = 0·9518 å, α = 107·49°, and the experimental r _e = 0·9572 å, α = 104·52°.

Force constants were found to be quite insensitive to variation in the basis functions, all three sets giving almost the same result. On the other hand, the dipole moment derivative is very sensitive.     

两种烷基碘化物分子C—I键解离的从头计算

分别采用多组态自洽场方法和二阶多组态准简并微扰论方法,计算了烷基碘化物分子CF₃I和C₂H₂F₃I沿C—I键的绝热势能曲线和垂直激发能. 结果发现,这两种分子的低激发态均为排斥态;基态的解离能分别为2.473eV和2.835eV,其中前者与实验结果符合较好. 关键词： 烷基碘化物分子 解离能 势能曲线     

Ab initio fermi surface calculation for charge-density wave instability in transition metal oxide bronzes

The electronic structure of the charge density wave (CDW) bronze (PO2)(4)(WO3)(2m), m = 4, is determined using ab initio density functional theory. The calculation shows that the Fermi surface (FS) consists in the superposition of three one-dimensional FS's associated with three types of chains. The q dependence of the electronic response function calculated from the electronic structure quantitatively accounts for the anisotropy of the fluctuations probed by x-ray diffuse scattering. The results validate the hidden nesting mechanism proposed for the CDW transitions in this series of bronzes.     

Ab initio calculations of multipole moments,polarizabilities and long-range interaction coefficients for the azabenzene molecules

Using LCAO-SCF wave functions on the monomers and a non-empirical Unsöld procedure for the second-order properties we have calculated the (2 ^l ) multipole moments (up to l=6), the (l,l') multipole polarizabilities (up to l + l' = 6) and the related long-range coefficients describing the electrostatic, induction and dispersion interactions for the different azabenzene molecules. The agreement with available experimental data is good, in particular for the dipole polarizabilities. The anisotropy of the long-range interaction potential is dominated by the electrostatic contributions, although the dispersion terms, especially the mixed-pole terms (l≠l') for even n (C₈, C₁₀), also contribute significantly; the induction energy is rather small. The π contributions to the polarizabilities and the dispersion interactions are found to be larger than earlier estimates. Moreover, it is shown by calculating the dipole polarizabilities of some (aza)naphthalenes and (aza)anthracenes, that a bond polarizability model can be applied effectively only if the delocalized π electrons are considered separately from the σ electrons.     

Nonempirical and quasi-classical approaches to the calculation of the electronic transition dipole moments

The dependence of the electronic transition dipole moment on the internuclear separation is calculated nonempirically for the Meinel band of the N ₂ ⁺ molecular ion using the Gaussian 98 software package with different basis sets. The results are compared with the dependences obtainedby the semiempirical methods. The basic relationships of the R-centroid method are derived, and the quasi-classical nature of this method is demonstrated. It is confirmed that the dependence of the electronic transition dipole moment on the internuclear separation is described most reliably by using the semiempirical methods. The vibronic transition dipole moment is shown to be an oscillating function of the vibrational quantum number v1 (with v2=const) or v2 (with v1=const).     

Spin-vibronic transition moments and rotational intensities in doublet-quartet transitions in asymmetric top molecules

Symmetry and time reversal arguments allow the rigorous determination of the nonvanishing and independent spin-vibronic transition moments for doublet-quartet transitions in asymmetric top molecules. Less strict additional relations, leading to a smaller number of independent parameters, are derived by considering an insight of the intensity borrowing mechanism in the case of weak spin-orbit interactions. In this case it is shown that there are either two or three independent transition moments in orthorhombic molecules, depending on the symmetry species of the vibronic wavefunctions involved in the transition.Case (b) selection rules are derived, and it is shown that rotational intensities in orthorhombic molecules can be obtained in all cases by squaring certain sums of either all real or all imaginary terms. A diagrammatical method is devised to identify the form and polarization of the nonvanishing transition moments as well as the symmetry species of the products of those vibronic pairs whose spin-orbit mixing contributes to a given transition moment.     

Ab initio calculation of the lowest ionization potential and transition energies of methane

The lowest ionization potential and transition energies of methane are calculated by a second-order perturbation expansion, using a limited basis of gaussian-type orbitals. An attempt is made to rationalize the choice of basis atomic orbitals. This procedure yields 13·8 eV for the first ionization potential and 10·4 eV for the lowest allowed transition provided a diffuse molecular orbital is added to describe the excited state (the experimental values are 13·6 and 9·7 eV). These two values include contributions of -1·0 and -0·70 eV, respectively, from an approximate optimization of the basis atomic orbitals and of +0·50 and +0·25 eV from electron correlation.     

Kinetics of dipole moments of polyatomic molecules

The relations that link the time dependences of the dipole moments of the ground and excited states of a molecular system whose charge distribution is nonstationary with the correlation functions of the shift of the absorption and emission spectra of this system are derived on the basis of of the well-known equations of solvatochromism. The calculated dependences of the kinetics of the dipole moments of the excited singlet states of dimethylaminobenzonitrile and 4-dimethylamino-4′-cyanostilbene in some polar solvents are presented.     

On the determination of small electric dipole moments of excited electronic states in diatomic molecules

A new method is proposed for the determination of small electric-dipole moments in diatomic molecules by measuring the induced transitions due to crossed electric and magnetic fields. A theoretical treatment is given for states belonging to Hund's cases (a) and (b), and for states in the intermediate coupling case between Hund's cases (a) and (b). The method is restricted to non-Σ states.