“Exact” and Approximate Methods for Bayesian Inference: Stochastic Volatility Case Study

We conduct a case study in which we empirically illustrate the performance of different classes of Bayesian inference methods to estimate stochastic volatility models. In particular, we consider how different particle filtering methods affect the variance of the estimated likelihood. We review and compare particle Markov Chain Monte Carlo (MCMC), RMHMC, fixed-form variational Bayes, and integrated nested Laplace approximation to estimate the posterior distribution of the parameters. Additionally, we conduct the review from the point of view of whether these methods are (1) easily adaptable to different model specifications; (2) adaptable to higher dimensions of the model in a straightforward way; (3) feasible in the multivariate case. We show that when using the stochastic volatility model for methods comparison, various data-generating processes have to be considered to make a fair assessment of the methods. Finally, we present a challenging specification of the multivariate stochastic volatility model, which is rarely used to illustrate the methods but constitutes an important practical application.     

Diabatic investigation for the NaRb molecule

An extensive diabatic investigation of the NaRb species has been carried out for all excited states up to the ionic limit Na^‐Rb⁺. An ab initio calculation founded on the pseudopotential, core polarization potential operators and full configuration interaction has been used with an efficient diabatization method involving a combination of variational effective hamiltonian theory and an effective overlap matrix. Diabatic potential energy curves and electric dipole moments (permanent and transition) for all the symmetries Σ⁺, Π, and Δ have been studied for the first time. Thanks to a unitary rotation matrix, the examination of the diabatic permanent dipole moment (PDM) has shown the ionic feature clearly seen in the diabatic ¹Σ⁺ potential curves and confirming the high imprint of the Na^‐Rb⁺ ionic state in the adiabatic representation. Diabatic transition dipole moments have also been computed. Real crossings have been shown for the diabatic PDM, locating the avoided crossings between the corresponding adiabatic energy curves.     

Spin‐Hamiltonian parameters and local lattice structure for Pd(I) center in γ‐irradiated bis(acetylacetonato)palladium(II)

This paper reports on a theoretical analysis of spin‐Hamiltonian parameters and local lattice structure for Pd(I) center in γ‐irradiated Pd(II)(acac)₂. Through the crystal‐ and ligand‐field theory, the microscopic spin‐Hamiltonian parameters and local molecular structure for Pd(I) center in the γ‐irradiated Pd(II)(acac)₂ system have been studied by using the high‐order perturbation formulas and Newman's superposition model. Based on these calculations, it was found that the distance of the metal‐ligand bonds in the square planar complex for Pd(I) center in the γ‐irradiated Pd(II)(acac)₂ system increases by 0.1Å. To understand the detailed physical and chemical properties of the [Pd(I)(acac)₂]^2– complex, the contributions of the spin‐orbit coupling of ligand to spin‐Hamiltonian parameters for Pd(I) ion are considered. The theoretical results are in reasonable agreement with the experimental values. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

15N216O在1650-3450 cm-1的高分辨红外光谱

采用傅里叶变换红外光谱仪记录了富含¹⁵N₂¹⁶O同位素的一氧化二氮样品在1650-3450 cm^-1波段的高分辨振转光谱,得到了该同位素分子超过7300吸收谱线位置的实验值,经分析实验精确度好于5.0×10^-4 cm^-1. 基于有效哈密顿量模型预测和带带转动分析,确定了所有吸收线的归属;获得了29个新吸收带的振转光谱参数,并优化了其他44个吸收带的光谱参数值. 并且发现有效哈     

Detection and analysis of new bands of O3 by CRDS between 6500 and 7300 cm

The absorption spectrum of the ¹⁶O₃ isotopologue of ozone has been recorded in the 7000-7920 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy. This report is devoted to the analyses of the 7065-7300 cm⁻¹ region dominated by the ν₁ + 2ν₂ + 5ν₃ and ν₁ + 5ν₂ + 3ν₃ A-type bands at 7130.8 and 7286.8 cm⁻¹ respectively. 289 transitions were assigned to the ν₁ + 2ν₂ + 5ν₃ band. The corresponding line positions were modeled with an effective Hamiltonian involving Coriolis resonance interactions between the (1 2 5) upper state and the (4 4 0), (0 2 6) and (6 1 0) dark states, and an anharmonic resonance interaction with the (2 0 5) state. The very strong interaction (up to 50% mixing of the wavefunctions) between the (1 2 5) and (6 1 0) states leads to the observation of two extra lines of the 6ν₁ + ν₂ band due to a resonance intensity transfer. 213 transitions of the ν₁ + 5ν₂ + 3ν₃ band were assigned and modeled taking into account a Coriolis resonance interaction with the (3 6 0) state.We take the opportunity of the present work to report the analysis of the very weak 4ν₂ + 4ν₃ B-type band at 6506.1 cm⁻¹ which was assigned from previously recorded CRDS spectra. 286 transitions were modeled using the effective Hamiltonian approach.The dipole transition moment parameters of the three analyzed bands were determined by a least-squares fit to the measured line intensities. For the three studied band systems, the effective Hamiltonian and transition moment operator parameters were used to generate line lists provided as Supplementary Materials.     

在群论框架下电子三重态与声子耦合的理论研究

本文基于绝热近似和群论导出了电声耦合系统的哈密顿量的一般形式,讨论了电声耦合系统中的电子算符和活跃的声子模式. 应用幺正平移变换和能量最小化方法,进一步计算了正四面体群下T*(e+t₂)杨-泰勒系统中的激发态能量,从对称性的角度分析了T₁电子态的能级分裂以及晶格体系的对称性破缺,得出了对称性的破缺方式和电声耦合系统密切相关的结论. 结果表明:通过群论与对称性分析完全可以定性地解释由于电声耦合所造成的简并电子 关键词： 电声耦合 杨-泰勒畸变 活跃的杨-泰勒声子模式 电声耦合哈密顿量     

On the extendedness of eigenstates in a hierarchical lattice: A critical view

We take a critical view at the basic definition of extended single particle states in a non-translationally invariant system. For this, we present the case of a hierarchical lattice and incorporate long range interactions that are also distributed in a hierarchical fashion. We show that it is possible to explicitly construct eigenstates with constant amplitudes (normalized to unity) at every lattice point for special values of the electron-energy. However, the end-to-end transmission, corresponding to the above energy of the electron in such a hierarchical system depends strongly on a special correlation between the numerical values of the parameters of the Hamiltonian. Keeping the energy and the distribution of the amplitudes invariant, one can transform the lattice from conducting to insulating simply by tuning the numerical values of the long range interaction. The values of these interactions themselves display a fractal character.     

Polynomial integrability of the Hamiltonian systems with homogeneous potential of degree − 3

In this paper, we study the polynomial integrability of natural Hamiltonian systems with two degrees of freedom having a homogeneous potential of degree k given either by a polynomial, or by an inverse of a polynomial. For k=−2,−1,…,3,4, their polynomial integrability has been characterized. Here, we have two main results. First, we characterize the polynomial integrability of those Hamiltonian systems with homogeneous potential of degree −3. Second, we extend a relation between the nontrivial eigenvalues of the Hessian of the potential calculated at a Darboux point to a family of Hamiltonian systems with potentials given by an inverse of a homogeneous polynomial. This relation was known for such Hamiltonian systems with homogeneous polynomial potentials. Finally, we present three open problems related with the polynomial integrability of Hamiltonian systems with a rational potential.     

Optimized t-expansion method for the Rabi Hamiltonian

A polemic arose recently about the applicability of the t-expansion method to the calculation of the ground state energy E₀ of the Rabi model. For specific choices of the trial function and very large number of involved connected moments, the t-expansion results are rather poor and exhibit considerable oscillations. In this Letter, we formulate the t-expansion method for trial functions containing two free parameters which capture two exactly solvable limits of the Rabi Hamiltonian. At each order of the t-series, E₀ is assumed to be stationary with respect to the free parameters. A high accuracy of E₀ estimates is achieved for small numbers (5 or 6) of involved connected moments, the relative error being smaller than ¹⁰−4 (0.01%) within the whole parameter space of the Rabi Hamiltonian. A special symmetrization of the trial function enables us to calculate also the first excited energy E₁, with the relative error smaller than ¹⁰−2 (1%).     

Singular densities,test particles and generalized Hamiltonian systems in general relativity

We derive the motion equations and the structure equations of neutral and charged test particles, starting from the gravitational field equations. The method consists in the application of conservation laws to singular tensor densities, which represent regions of strong matter concentration. Moreover, a Hamiltonian formulation of the particle equations is given, in the form of implicit differential equations generated by Hamiltonian Morse families.