Calculation of vibrational HDO energy levels: Analysis of perturbation theory series

Series of the Rayleigh-Schrödinger perturbation theory are analyzed and summated by the example of the HD¹⁶O molecule for vibrational energy levels. Particular attention is given to determining the location of singularities-branching points corresponding to the intersection of levels in the complex plane. Numerical analysis demonstrates the divergence of the series for states involved in the Fermi resonance; however, summation by the method of Padé-Hermite approximants makes it possible to reconstruct the levels by coefficients of the series with sufficient accuracy. It is found that resonance-coupled states have common branching points, which leads to the coincidence of series’ coefficients in high orders. Branching points’ characteristics permitting one to obtain a comparatively simple representation of high order corrections are determined.     

Calculation of rotationally vibrational energy of HDO molecule

The anharmonic constants and the constants of rotation-vibration interaction have been calculated for an asymmetrical non-linear three atomic molecule on the assumption that Pliva's potential function for polyatomic molecules is valid.     

The perturbation series for φ 3 4 field theory is divergent

We prove in a rigorous way the statement of the title.     

On the summation of divergent perturbation series in quantum mechanics and field theory

The possibility of recovering the Gell-Mann–Low function in the asymptotic strong-coupling regime by known first-order perturbation-theory (PT) terms β_n and their asymptotics as \(\tilde \beta _n \) as n → ∞ is investigated. Conditions are formulated that are necessary for recovering the required function at the physical level of rigor: (1) a large number of PT coefficients are known whose asymptotics has already been established, and (2) there is no intermediate asymptotics. Higher orders of PT, their asymptotic behavior, and power corrections are calculated in quantum mechanical problems that involve divergent PT series (including series for a funnel potential, the ? ₍₀₎ ⁴ model, and the Stark effect in a strong field). The scalar field theory ? ₍₄₎ ⁴ is considered in the \(\overline {MS} \) and MOM regularization schemes. It is shown that one cannot make any definite conclusion about the asymptotics of the Gell-Mann–Low function as g → ∞ on the basis of information available for the above theory.     

On the study of the vibrational energy levels of Arsine molecule

We compare two formalisms applied to the vibrational modes of the molecule of AsH₃ of C_3v molecular symmetry group. Indeed, the close stretching modes of this molecule may be considered as those of a three-dimensional oscillator whereas the bending modes may be considered either as a one-dimensional oscillator of symmetry A₁ and a two-dimensional oscillator of symmetry E or as an approximate three-dimensional oscillator. So, we have applied the U(p + 1) formalism to the both stretching and bending modes and introduced coupling terms acting on an appropriate coupled vibrational basis through a local mode formalism. We have then compared the result of our fitting with those obtained with the coupling of a local mode formalism adapted to the stretching vibrations with a normal mode formalism for the bending ones. Finally we compare our results with other methods recently proposed in the literature.     

Calculation of spin-density matrix by diagrammatic perturbation theory

A diagrammatic perturbation-theory method for direct calculation of spin-density matrix of open-shellN-electron systems described by the restricted Hartree-Fock one-particle functions is formulated. The formulae correct up to the second order of perturbation theory (second order in correlation effects) are presented. Their generalization to account for infinite summations of dominant correlation effects is simple, realized by making use of the so-called coupled cluster approach.     

Variational calculation of low-lying and excited vibrational levels of the water molecule

The variational method of calculating vibrational energy levels for triatomic molecules has been extended to determine the lowest 22 levels for H₂O, using an analytic form for the potential surface developed by Sorbie and Murrell. In addition, complete ab initio calculations of the fundamental frequencies for H₂O have been carried out using extensive configuration interaction forms for the potential. They are predicted to be 3720, 1629, and 3807 cm^?1, to be compared with experimental values of 3656, 1597, and 3754 cm^?1. Also discussed is how the variational method may be extended to allow the calculation of vibrational energy levels for larger molecules.     

Accurate energy levels for the anharmonic oscillator and a summable series for the double-well potential in perturbation theory

We introduce a generalization of Wick-ordering which maps the anharmonic oscillator (AO) Hamiltonian for mass m and coupling λ exactly into a “Wick-ordered” Hamiltonian with an effective mass M which is a simple analytic function of λ and m. The effective coupling $\text{Λ =}\text{λ}\text{M}{}^3$ is bounded. We transform the AO perturbation series in λ into one in Λ. This series may then be summed using Borel summation methods. We also introduce a new summation method for the AO series (which is a practical necessity to obtain accurate energy levels of the excited states). We obtain a numerical accuracy for $\text{(E}{}_{\mathrm{PT}}\text{? E}{}_{\mathrm{exact}}\text{)}\text{E}{}_{\mathrm{exact}}$ of at least 10^?7 (using 20 orders of perturbation theory) and 10^?3 (using only 2 orders of perturbation theory) for all couplings and all energy levels of the anharmonic oscillator. The methods are applicable also to the double-well potential (DWP, the AO with a negative mass-squared). The only change is that now the effective coupling is unbounded as λ → 0. The series in Λ is, however, still summable. The relative accuracy in the energy levels for 20 orders of perturbation theory varies from 10^?7 for large coupling to 1% at λ = 0.1 and to 10% at λ = .05. We also present results for the sextic oscillator.     

Heterogeneous relaxation of molecule vibrational energy on metals

A mechanism of heterogeneous relaxation of a molecule vibrational energy on metal via conduction electrons is proposed. The probability of vibrational transition W of a molecule adsorbed on metal surface is calculated. The not very sharp dependence of W on the distance between the molecule and the metal surface, on metal parameters and on the molecular vibrational quantum provides a satisfactory explanation of the experimental data available.     

The vibrational energy levels of ammonia

A variational 6-dimensional method is used to determine the low lying vibrational energy levels of ammonia. The six internal coordinates were chosen to be appropriate for the symmetry and inversion motion of the molecule; they were the three NH bond lengths, r1, r2, r3, the unique angle β which each bond makes with the trisector of them, and two (of the three) angles, θ2 and θ3, between the bonds when projected on to a plane perpendicular to the trisector. The Wilson G matrix was determined for these internal coordinates both by computer algebra and by hand. An appropriate Jacobian for the motion was determined and the full Hermitian kinetic energy operator was obtained using the Podolsky transformation. Expansion functions were in the usual product form. Special attention was given to the θ2, θ3 expansion functions so that appropriate A1, A2 and E symmetry vibrational modes were obtained explicitly. Matrix elements of the kinetic energy operator were expressed in terms of one-dimensional integrals.Variational calculations have been performed with two six-dimensional surfaces: (i) that due to Martin, Lee and Taylor; and (ii) that due to Spirko and Kraemer. Although some of the vibrational levels for both surfaces are accurate, both have inadequacies: (a) because it is a Taylor expansion about an equilibrium, based on ab initio calculations, with no attention paid to planarity; and (b) because the non-inversion part of the surface was treated perturbatively in its derivation, and in fact some of the quartic displacement powers have negative coefficients. Therefore, neither surface gave good results overall, and there is a need for a refined 6 dimensional NH3 surface.     

Large-order estimates for ground-state energy perturbation series

A general treatment is given, using path integral methods, of obtaining accurate estimates on the rate of growth at large order of the perturbation coefficients for the lowest eigenvalue (ground-state energy) of a large class of anharmonic oscillators. Simple sufficient conditions are given on the potentialV(x) so that accurate upper and lower bounds on the perturbation coefficients may be derived. Several examples are given which generalize previous results. Examples from Euclidean quantum field theory are also considered.This paper is dedicated to the memory of Mark Kac.     

United-atom projected perturbation theory for a homonuclear diatomic molecule

It is observed that the Byers-Brown united-atom perturbation theory corresponds to a particular version of the perturbation theory for projected states. Another, more localized version of the theory is suggested and tested on a solvable model.     

Self-consistent perturbation theory for the vibrational spectra of certain disordered systems

The effect of coupling parameter fluctuations (quantitative disorder) on the vibrational spectrum of a solid is investigated. Since small deviations from crystalline order already turn out to lead to considerable broadening of the crystalline spectrum, a self-consistent perturbation scheme is developed similar to the coherent potential approximation for electronic systems. An approximate equation is obtained in which disorder is described in terms of a single dimensionless parameter which is a measure of the mean square fractional deviations of the coupling parameters from their average values. The equation is solved self-consistently by iteration. The final result is a convolution expression for the amorphous spectrum in which all van Hove singularities are smeared out except the ones at zero frequency and at the upper cutoff of the spectrum. Numerical results are obtained for silicon using a Keating crystalline density of states and assuming that the average values of the coupling parameters are identical to the crystalline ones. The maxima of the crystalline spectrum are broadened but qualitatively retained to a larger extent than in a simple convolution of the spectrum with a Gaussian.     

Braneworld cosmological perturbation theory at low energy

Homogeneous cosmology in the braneworld can be studied without solving bulk equations of motion explicitly. The reason is simply because the symmetry of the spacetime restricts possible corrections in the 4-dimensional effective equations of motion. It would be great if we could analyze cosmological perturbations without solving the bulk. For this purpose, we combine the geometrical approach and the low energy gradient expansion method to derive the 4-dimensional effective action. Given our effective action, the standard procedure to obtain the cosmological perturbation theory can be utilized and the temperature anisotropy of the cosmic background radiation can be computed without solving the bulk equations of motion explicitly.     

The impact of vibrational wave function on low energy electron vibrational scattering from nitrogen molecule

The vibrational wave function of the target theoretically plays an important role in the calculation of vibrational excitation cross sections. By a careful study of the differential cross sections resulting from different vibrational wave functions we find that cross sections are susceptible to vibrational wave functions. Minor changes in the vibration wave function may cause a significant change in the cross section. Even more surprising is that by selecting a few numbers of potential models(which determine the vibrational wave functions) we can often calculate the differential scattering cross section in much closer agreement with experiment in the framework of body-frame vibrational close-coupling theory, which suggest that an accurate potential energy may play a more important role in scattering than we thought before.