Convergence properties of methods for effective operator calculations studied in a simple many-body model

Several methods for effective interaction and operator calculations based on the Rayleigh-Schrödinger and Brillouin-Wigner perturbation expansions are studied. Special emphasis is given to the use of Padé approximants for effective operator calculations. The convergence properties of the methods are studied numerically in a Lipkin many-body model. Among the various methods using Padé-approximants, the method based on a variational approach in the BW scheme is found to give most encouraging results for the present model.     

Quantum corrections to the radial distribution function of a fluid

Many-body effects in the X¹σ⁺ states of the hydrogen fluoride, lithium fluoride and boron fluoride molecules are investigated. Using diagrammatic perturbation theory, two, three and four-body contributions to the electronic energy are calculated to third order within the algebraic approximation. Many-body effects are found to be very significant. Two zeroth-order hamiltonians are employed and the convergence of the resulting perturbative expansions are compared. The [2/1] Padé approximants to the energy are constructed. Upper bounds to the energy are determined by evaluating the Rayleigh quotient for the first-order perturbative wavefunction.     

Calculations of the static polarizability and hyperpolarizability of the LiF molecule including vibrational contributions

The static dipole moment, polarizability and first hyperpolarizability of the LiF molecule have been calculated, including vibrational corrections, using Möller—Plesset perturbation theory and coupled cluster methods. The results show that the vibrational corrections, dominated by the nuclear relaxation term, are as important for the calculations of the polarizability and hyperpolarizability as the electronic contribution, and that the electron correlation effects play an important role in the calculations of both electronic and vibrational contributions for these static properties.     

Perturbation theory and Padé approximants in realistic large-matrix models of the nuclear effective interaction

Realistic extended shell-model calculations are used to construct exact effective Hamiltonians, the perturbation series for the effective Hamiltonian to any order, and the [N+1, N] Padé approximants to the series. It is found that the Padé approximants give reliable results even when the series diverge, but that for both convergent and divergent series reasonably accurate results can be obtained only in fifth, or even seventh order. In addition, the poles of the low-order Padé approximants are not always reliable indicators of singularities of the perturbation series. The perturbation series and Padé approximants for the Q-box (energy-dependent effective Hamiltonian) are no more accurate in low orders than those for the usual effective Hamiltonian. Explicit formulas for the matrix Padé approximants are given in an appendix.     

Thermodynamic perturbation theory for multipolar and ionic liquids

We extend earlier work of ours on the use of Padé approximants in the theory of multipolar and ionic potentials. The new features are (i) extension of our work to mixed multipole terms and inclusion of polarizability, (ii) formulation and implementation of a systematic means of getting analytic approximations for all the two-body and three-body terms appearing in the theory, (iii) assessment of the ionic Padé results in the low-concentration region important in ionic-solution applications, (iv) use of the Padé in a mixed perturbation theory of improved accuracy in that low-concentration regime. The results of (iii) and (iv) are used to study the remarkable lowdensity charged-sphere critical point recently discovered by Stell, Wu, and Larsen.     

On the dipole moment of three identical spherical atoms

Martin's perturbation theory result [2] for the dipole moment of three identical spherical atoms at large separations is shown to simplify: There are two contributions to this three-atom dipole and the strength of each factors into a product of the dipole polarizability of one atom and a two-atom average of dipole and quadrupole matrix elements. The simplified results are used to obtain an improved evaluation of the three-atom dipole of three He atoms, employing extensive pseudo-spectral representations of the dipole and quadrupole excitations.     

Lattice gauge theory calculations using an improved strong-coupling expansion and matrix Padé approximants

Matrix methods are used to obtain better convergence of low-order lattice calculations. Strong-coupling expansions for the Hamiltonian matrix in a non-degenerate subspace of states are extrapolated to zero lattice spacing using matrix Padé approximants. The method is applied first to the massive Schwinger model and the continuum estimates from different fourth-order calculations compared. Then it is used to calculate the ratios of the π, ? and ω meson masses to the nucleon mass in a Hamiltonian lattice formulation of QCD.     

Calculations of the polarizability and hyperpolarizability of the NaH molecule including vibrational corrections

In this work we present results for the dipole moment, polarizability and first hyperpolarizability of the NaH molecule obtained through the many-body perturbation-theory, coupled cluster and quadratic configuration interaction methods, including vibrational corrections. It is shown that the nuclear relaxation contribution is of fundamental importance for both polarizability and first hyperpolarizability of this system. Besides, inclusion of electron correlation effects changes appreciably the size of this contribution. In addition, our results show that the curvature contribution does not alter significantly the values obtained for the polarizability.     

Calculation of vibrational energy levels of triatomic molecules with the C2v and Cs symmetries by summing divergent series of the Rayleigh-Schr?dinger perturbation theory

The Rayleigh-Schr?dinger perturbation theory is applied to calculation of vibrational energy levels of triatomic molecules with the C _2v and C _s symmetries: SO₂, H₂S, F₂O, HOF, HOCl, and DOCl. Particular attention is given to the states coupled by anharmonic resonances; for such states, the perturbation theory series diverge. To sum these series, the known methods of Padé, Padé-Borel, and Padé-Hermite and the method of power moments are used. For low-lying levels, all the summation methods give satisfactory results, while the method of quadratic Padé-Hermite approximants appears to be more efficient for high-excited states. Using these approximants, the structure of singularities of the vibrational energy, as a function in the complex plane, is studied.     

The multipole polarizabilities and hyperpolarizabilities of the water molecule in liquid state: an ab initio study

A charge perturbation variant of the finite-field method has been used to calculate dipole and quadrupole moments, dipole polarizability, hyper- and principal components of high-order polarizabilities of the water molecule in gas and in liquid phase conditions. Calculations were performed for the ground-state water molecule at the MP2 and MP4 levels of theory. The gas phase values determined allow our methodology for extracting polarizabilities to be tested and a properly balanced, moderate-sized basis set to be selected; the results obtained are in very good agreement with experiment and the most accurate previous theoretical estimates. A local field approach is introduced to mimic the electrostatic environment experienced by a water molecule in the liquid. Within this approach, sets of fixed charges are used to generate the desired electric fields and field gradients. Three different liquid phase models and the corresponding sets of electrical properties are examined. The values obtained from these models and for gas-phase are compared. The magnitudes of the dipole and the quadrupole moments increase moving from gas to liquid phase, where the latter shows greater sensitivity to the choice of liquid model. For a liquid phase water molecule the first hyperpolarizability (β) and first higher polarizability (A) increase markedly, actually changing sign, the second hyperpolarizability (γ) also increases but much less dramatically, and components of the second high-order polarizability tensor (B) demonstrate a rearrangement of contributions. The values reported for the hyper- and high-order polarizability tensors are the first such theoretical estimates for liquid water.     

Effective conductivity for densely packed highly conducting cylinders

We study the effective heat conductivity λ₃ of a periodic square array of nearly touching cylinders of conductivity h, embedded in a matrix material of conductivity 1. We construct a sequence of two-point Padé approximants for the effective conductivity. As the basis for the construction we use the coefficients of the expansions of λ_e at h=1 and h=∞. The two-point Padé approximants form a sequence of rapidly converging upper and lower bounds on the effective conductivity.     

Optical and magnetic studies on the phosphorescent state of phthalazine in polar and non-polar hosts

The ground state potential energy curve for the beryllium dimer is calculated using non-degenerate many-body perturbation theory and the multi-configuration self-consistent-field/configuration interaction method. Quasi-degeneracy in this system makes it useful in exploring the limitation of the applicability of the non-degenerate formulation of diagrammatic many-body perturbation theory. Both methods are applied within the algebraic approximation defined by a contracted gaussian basis set of triple zeta quality. It is shown that non-degenerate perturbation theory can lead to a potential energy curve which is in close agreement with the configuration interaction curve when taken to third order in the energy and [2/1] Padé approximants constructed.     

Padé approximation methods applied to the intermolecular force series

The H(1s)-H⁺, He-He, H(1s)-H(1s) and H(1s)-H(2s) interactions are considered as model systems for investigating the use of the Padé approximation method in summing the R ^-1 intermolecular force series. Various Padé approximants and partial sums of the R ^-1 expansions of the second-order Coulomb interaction energies are compared with the corresponding non-expanded results for each interaction. The computations are based on Unsöld's average energy approximation and on exact results for the H(1s)-H interaction. The results indicate that the Padé approximation method is a simple, useful way to remove some of the difficulties associated with the slow rate of convergence of the R ^-1 force series but that it does not alleviate the problems associated with the asymptotic divergent nature of the series. The results for the H(1s)-H⁺ interaction illustrate a possible difficulty in using Unsöld's method in the calculation of interaction energies.     

类锂离子(Z=11～20) 1s22s-1s23p的跃迁能和振子强度

用全实加关联方法计算类锂离子(Z=11～20)偶极跃迁1s22s*"2S-1s23p*"2P1/2,3/2的跃迁能.非相对论能量用Rayleigh-Ritz变分法确定,相对论修正和质量极化效应用微扰论计算,还估算了来自量子电动力学效应的修正.得到的计算结果与现有的实验数据符合得很好,我们关于氯的类锂离子(Z=17)1s23p态的精细结构劈裂的计算结果揭示,相应的实验数据明显偏离等电子序列的物理规律.还算了1s22s-1s23p偶极跃迁的振子强度.     

类锂离子(Z=11～20)1s23p-1s2nd(n=6,7)的跃迁能和振子强度

用全实加关联(FCPC)方法计算类锂离予体系(Z=11～20)1s2nd(n=6,7)态的非相对论能量.相对论及质量极化效应对能量的修正用微扰论计算,量子电动力学(QED)修正利用有效核电荷方法估算.在此基础上计算了1s23p-1s2nd(n=6,7)的跃迁能及振子强度,对现有的关于1s2nd(n=6,7)态的精细结构的实验数据的可靠性提出质疑.     

An adaptable summation algorithm

A simple generalization of Wynn's ϵ algorithm is reported. The algorithm includes a parameter K, and yields Padé approximants at K = 1 and repeated Aitken transforms at K = 0. Test on several perturbation series show that the choice K = −1 leads to accurate estimates of perturbation sums.     

Vibrational corrections to electric properties of weakly bound systems

The pure electronic and vibrational contributions to electric dipole moments, dipole polarizabilities, and first hyperpolarizabilities have been evaluated for the HF and H₂O dimers. The zero-point vibrational average corrections to dipole moments and dipole polarizabilities turn out to be relatively small. However, the corresponding contributions to the first hyperpolarizability are found to be of the same magnitude as the pure electronic values. The so-called pure vibrational corrections to the dipole polarizability and first hyperpolarizability of hydrogen bonded dimers are exceptionally large and indicate that the perturbation theory method used for their evaluation fails to account properly for the high mechanical and electric anharmonicities present in these systems. The analysis of different harmonic and anharmonic contributions to the pure vibrational correction to the first hyperpolarizability shows explicitly the importance of the low frequency intermolecular modes.     

Two-loop two-point functions with masses: asymptotic expansions and Taylor series,in any dimension

In all mass cases needed for quark and gluon self-energies, the two-loop master diagram is expanded at large and smallq ², ind dimensions, using identities derived from integration by parts. Expansions are given, in terms of hypergeometric series, for all gluon diagrams and for all but one of the quark diagrams; expansions of the latter are obtained from differential equations. Padé approximants to truncations of the expansions are shown to be of great utility. As an application, we obtain the two-loop photon self-energy, for alld, and achieve highly accelerated convergence of its expansions in powers ofq ²/m ² orm ²/q ², ford=4.     

Effective dipole moment of rotational transitions of X 2 Y molecules

Contributions determining the rotational dependence of the effective dipole moment of molecules are calculated for the ground state of H₂S and H₂O molecules. The calculation is carried out in various ordering algorithms of perturbation theory. It is shown that the convergence of the effective dipole moment for the ground state of an H₂O molecule in the polynomial representation is rather slow in the rotational operator J _z (the convergence radius is K*≤17). Nonpolynomial forms of the dipole moment as a function of rotational operators are discussed.     

Derivation of effective spin models from a three band model for CuO-planes

The derivation of effective spin models describing the low energy magnetic properties of undoped CuO₂-planes is reinvestigated. Our study aims at a quantitative determination of the parameters of effective spin models from those of a multi-band model and is supposed to be relevant to the analysis of recent improved experimental data on the spin wave spectrum of La₂CuO₄. Starting from a conventional three-band model we determine the exchange couplings for the nearest and next-nearest neighbor Heisenberg exchange as well as for 4- and 6-spin exchange terms via a direct perturbation expansion up to 12th (14th for the 4-spin term) order with respect to the copper-oxygen hopping t_pd. Our results demonstrate that this perturbation expansion does not converge for hopping parameters of the relevant size. Well behaved extrapolations of the couplings are derived, however, in terms of Padé approximants. In order to check the significance of these results from the direct perturbation expansion we employ the Zhang-Rice reformulation of the three band model in terms of hybridizing oxygen Wannier orbitals centered at copper ion sites. In the Wannier notation the perturbation expansion is reorganized by an exact treatment of the strong site-diagonal hybridization. The perturbation expansion with respect to the weak intersite hybridizations is calculated up to 4th order for the Heisenberg coupling and up to 6th order for the 4-spin coupling. It shows excellent convergence and the results are in agreement with the Padé approximants of the direct expansion. The relevance of the 4-spin coupling as the leading correction to the nearest neighbor Heisenberg model is emphasized. Received 8 June 2001 / Received in final form 28 May 2002 Published online 19 July 2002