Coupled ab initio potential energy surfaces for the two lowest 2A′ electronic states of the C2H molecule

Realistic two-valued potential energy surfaces for the reaction C(³P) + CH(X²Π) → C₂ + H have been constructed from a set of high level ab initio data describing the first two ²A′ electronic states of the C₂H system. These states have linear equilibrium configurations, known as the X ²Σ⁺ and A²Π states, and are coupled by a conical intersection. They lead to the formation of C₂(X¹Σ⁺ _g) and C₂(a³Π_u) considering an adiabatic dissociation process. The ab initio calculations are of the multireference configuration interaction variety and were carried out using a polarized triple-zeta basis set. Using the ab initio adiabatic energies and the matrix elements of the dipole moment, a 2 × 2 diabatic representation of the electronic Hamiltonian was built. Each element of this Hamiltonian matrix was expressed within the double many-body expansion (DMBE) scheme which is based, in this case, on the extended Hartree-Fock approximate correlation energy model (EHFACE). The analytical adiabatic potential energy surfaces are then obtained as the eigenvalues of this matrix, and display correctly the Σ/Π conical intersection. Moreover, the non-adiabatic couplings given by our analytical model are compared with the ab initio ones, and good qualitative agreement is observed.     

Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules

Stretching vibrational band intensities of XH₃ (X=N, Sb) molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model.The dipole moment surfaces of NH₃ and SbH₃ are calculated with the density functional theory and at the correlated MP2 level,respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides (NH₃, PH₃,AsH₃ and SbH₃) are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.     

MRCI+Q理论研究SiSe分子X1Σ+和A1Π电子态的光谱常数和分子常数

采用Davidson修正的内收缩多参考组态相互作用方法(MRCI+Q)及相关一致基aug-cc-pV5Z和aug-cc-pVQZ分别计算了SiSe分子X¹Σ⁺和A¹Π电子态的势能曲线. 为提高势能曲线的计算精度, 利用两点总能量外推公式, 将两个电子态的势能曲线外推至完全基组极限, 并对其进行了标量相对论修正, 相对论效应是在cc-pV5Z基组水平下使用三级Douglas-Kroll-Hess哈密顿算符计算的. 利用MRCI+Q/Q5+DK理论水平的势能曲线获得了这两个态的光谱常数(T_e, D_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e和α_e)和J=0时前30个振动态的B_υ和D_υ等分子常数. 其值与已有的实验结果非常一致. 本文得到的光谱常数和分子常数达到了很高精度, 能为进一步的光谱实验和理论研究提供可靠参考. 关键词： 势能曲线 基组外推和标量相对论修正 光谱常数 分子常数     

The v 1 and v 3 bands of ND3

High resolution (0.004cm^-1 instrumental bandwidth) interferometric Fourier transform infrared spectra of ¹⁴ND₃ were obtained on a BOMEM DA002 spectrometer under essentially Doppler limited conditions. An analysis is reported of the ND₃ stretching fundamentals with band centres at [EQUATION]₁ ⁰ (s ← a) = (2420.056 ± 0.001)cm^?1, [EQUATION]₁ ⁰(a ← s) = (2420.650 ± 0.001)cm^?1, [EQUATION]₃ ⁰(a ← a) = (2563.8840 ± 0:0005)cm^?1 and [EQUATION]₃ ⁰ (s ← s) = (2563.9161 ± 0.0005)cm^?1, with inversion tunnelling splittings Δ[EQUATION]₁ = 0.5412cm^?1 and Δ[EQUATION]₃ = 0.0209cm^?1 in the vibrationally excited levels. About 50 parameters of the effective Hamiltonian for this band system could be determined accurately. Assignments were established with certainty by means of ground state combination differences. The results are important for and are discussed in relation to the mode selective inhibition and promotion of inversion at the nitrogen atom by exciting ND stretching vibrations, and treatments of isotope e? ects on inversion of ammonia by means of effective Hamiltonians and true molecular Hamiltonians on high dimensional potential hypersurfaces.     

High-resolution FTIR spectroscopy of the Coriolis interacting nu3 and nu9 fundamentals of methylene fluoride-d2

The Fourier transform infrared spectrum of the υ ₃ and υ ₉ bands of methylene fluoride-d ₂ (CD₂F₂) has been recorded with an unapodized resolution of 0.0024cm^-1 in the frequency range 970-1080cm^-1. These two bands with band centres approximately 26 cm^-1 apart were mutually coupled by Coriolis interactions. By fitting a total of 1639 infrared transitions of both υ ₃ and υ ₉ with a standard deviation of 0.00084cm^-1 S/S using a Watson's A-reduced Hamiltonian in the I ^r representation with the inclusion of a first order c-type Coriolis resonance term, two sets of rovibrational constants for υ ₃ = 1 and υ ₉ = 1 states were derived. The υ ₃ band is B-type while the υ9 band is A-type with band centres at 1030.1573 ± 0.0003 and 1003.7435 ± 0.0001cm^-1, respectively.     

The infrared spectrum of isothiazole in the range 600–1500 cm−1, including a high-resolution study of the v 11(A′) band at 818 cm−1 and the v 16(A″) band at 727 cm−1, together with ab initio studies of the full spectrum

Abstract

The gas-phase high-resolution infrared spectrum of isothiazole in the range 600–1500 cm^?1 has been recorded, and revised band centres obtained for a number of vibrations. An analysis of the v ₁₁(A′) band at 818 cm^?1 and the v ₁₆(A″) band at 727 cm^?1 has been performed, using the Watson Hamiltonian, A-reduction, III^r representation. These were combined with previous microwave spectral data to provide combined analyses for rotational constants and quartic centrifugal distortion constants Δ _J , Δ _JK , Δ _K , δ _j and δ _K . These extend the knowledge derived from previous microwave and IR spectral studies. The equilibrium structures and the derived harmonic frequencies were calculated by ab initio methods, using a variety of basis sets with MP2, MP4 and CCSD(T) methods, and a comparison of these with experimental data is discussed. At a pragmatic level, the closest correlation of the rotational constants with experiment is not obtained with the most sophisticated methodology. Similarly, the vibration frequencies and intensities also vary strongly with the procedure. In particular, we found that the cc-pVTZ+MP2 results probably provide the best numerical comparison with experimental IR data for this molecule.     

The infrared spectrum of isoxazole in the range 600–1400 cm−l,including a high-resolution study of the v 7(A′) band at 1370.9 cm−1 and the v 16(A″) band at 764.9 cm−l,together with ab initio studies of the full spectrum

Abstract

The high resolution infrared gas phase spectrum of isoxazole in the range 600–1400 cm^?1 has been recorded and more precise centres obtained for a number of bands; analyses of the v ₇(A′) band at 1370.9cm^?1 and the v ₁₆(A″) band at 764.9cm^?1 have been performed. Use of the Watson Hamiltonian, A-reduction, III^r-representation and simultaneous analysis of the present IR and previous microwave data, has led to rotation constants and quartic centrifugal distortion constants Δ _J , Δ _JK , ΔK, δ _J and δ _K for the ground state and for the v ₁₆ vibrationally excited states. The equilibrium structures and the derived harmonic frequencies have been calculated by ab initio methods using triple zeta+polarization (TZVP) and cc-pVTZ basis sets, with MP2, MP4 and CCSD(T) methods. At each methodology, for closest numerical agreement between the calculated and observed rotation constants, the optimum basis set seems to be TZVP rather than cc-pVTZ basis sets. However, the order of the highest A″ and lowest A′ symmetry vibrations is only resolved by the cc-pVTZ basis set with the MP4 methodology, which does generate the experimental sequence (v ₁₄>v ₁₃) The CCSD(T) methodology does not lead to significant difference over either MP2 or MP4 with the TZVP basis set.     

Vibronic coupling in the first four electronic states of CH2F+2

Vibronic coupling in the energetically lowest first four electronic states of CH₂F⁺₂ is studied in this paper. A model 4×4 Hamiltonian is constructed in a diabatic electronic representation employing normal coordinates of vibrational modes and standard vibronic coupling theory. Extensive ab initio quantum chemistry calculations are carried out to determine the parameters of the Hamiltonian and energetic ordering of the electronic states. The topographical features of the latter are examined at length and several conical intersections are established. Nuclear dynamics calculations on coupled electronic states are carried out from first principles by propagating wave packet. Theoretically calculated broad band vibronic structure of the four states are found to be in good accord with the experimental results.     

Theory of substitutional alloys of intermediate valence systems: Concentration and temperature dependence of the static magnetic susceptibility

The effect of alloying in intermediate valence compounds is studied within an extended version of the Anderson model which takes into account substitutional disorder of the rare earth ions. In particular, we concentrate on modifications of the conduction band, describe them by an effective shift in the Fermi energy, and consider its influence on the mixed valence behaviour. By applying the alloy analog approximation to the manyparticle Hamiltonian describing the local magnetic 4f shells, the complete effective Hamiltonian is that of a ternary alloy. This problem is solved within the coherent potential approximation and the static magnetic susceptibility is calculated as a function of temperature and disorder. Depending on the shift of the Fermi energy with respect to the 4f levels, qualitatively different behaviour is obtained which corresponds very well with magnetic measurements on different Yb alloys. The model yields an inverse proportionality between the susceptibility atT=0 and the temperatureT _M of the susceptibility maximum as functions of the disorder.Work performed within the research program of the Sonderfor-schungsbereich 125 Aachen-Jülich-Köln     

Microscopic structure of <Superscript>126</Superscript>Ba in IBM terms

The yrast band of the nonaxially deformed ¹²⁶Ba nucleus is described by the Hamiltonian of the interaction boson model. Its parameters are calculated on the basis of a microscopic theory within a spherical mean field, and residual interactions that include pairing and multipole factorized forces. Each state of the yrast band is considered independently of others, allowing us to study variations in the superfluid properties of the nucleus and the quasiparticle structure of collective D phonons with spin. The calculations are performed in an expanded configuration space that includes the collective D phonon states, and noncollective states in which an additional phonon of positive parity whose spin assumes values of 0 to 6 is present along with the D phonons. It is shown that the collective Hamiltonian parameters cannot be reproduced without considering the effect of the noncollective states.     

Investigations on the g factors of the ground and excited states for Cu2+ ions in ZnO crystal

The g factors g _// and g _⊥ of the ground Γ₆(² T ₂) and excited Γ_4,5(² E), Γ₆(² E) states for trigonal Cu²⁺ centres in ZnO crystals are calculated from three theoretical methods, the complete diagonalization (of the energy matrix) method, the second-order perturbation method (PTM-I) and the simplified second-order perturbation method (PTM-II, this method was described in an earlier paper). These methods are based on the cluster approach in which the spin-orbit coupling parameters ζ, ζ′ and the orbital reduction factors k, k′ are calculated from a semi-empirical molecular orbital method. The crystal-field parameters used in the calculations are obtained from the superposition model and so the defect structure of Cu²⁺ centres in ZnO can be acquired. The calculated g factors from the three methods are in reasonable agreement with the experimental values and the defect structure of Cu²⁺ centres in ZnO is acquired. It appears that in some cases the approximate PTM can be applied in the studies of g factors of various states. The conditions that the PTM are ineffective are discussed.     

High resolution study of the 6ν1 P-H stretching band of the PHD2 molecule

The high resolution spectrum of a phosphine gas mixture containing PHD₂ was recorded at room temperature in the 12 550-12 770 cm⁻¹ region. A high sensitivity laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a Ti:sapphire ring laser was employed. More than 600 transitions were assigned to the 6ν₁ overtone band of PHD₂ up to J^max=20, K_a^max=6. A Hamiltonian model developed up to the octic centrifugal distortion terms was used. Seven rotational and centrifugal distortion parameters were fitted, the other ones being fixed to their values linearly extrapolated from ν₁ and 2ν₁. The derived parameters reproduce the initial data within the experimental uncertainties. The isolated character of the P-H bond is confirmed.     

The role of CDW gap on the magnetic phase transition in CMR materials

We propose a model to study the magnetic phase transition in the Colossal-Magneto-Resistance (CMR) material of general type R_1−x A _x MnO₃ (R = La, Sm, Nd; A = Ca, Sr, Ba). The model Hamiltonian consists of a Charge Density Wave (CDW) gap in the e _g -band and the strong magnetic field due to the spin ordering in the localized t _g core electrons. The Hamiltonian is solved by using Zubarev’s Green’s function technique to calculate CDW gap (Δ) and magnetization (M ^d ) in t _2g band. Both of them are solved self-consistently. Their combined effect on the temperature dependent magnetization (M ^c ) due to the e _g band electrons is investigated. Both the magnitude and the transition temperature of (M ^c ) are strongly influenced by both Δ and M ^d . Hence the hopping of the band electrons are strongly controlled by these two long range interactions. The results are discussed by varying the model parameters of the manganite system.      

CO2: Global Treatment of Vibrational–Rotational Spectra and First Observation of the 2ν1 + 5ν3 and ν1 + 2ν2 + 5ν3 Absorption Bands

The effective operator approach is applied to the calculation of both line positions and line intensities of the ¹³C¹⁶O₂ molecule. About 11 000 observed line positions of ¹³C¹⁶O₂ selected from the literature have been used to derive 84 parameters of a reduced effective Hamiltonian globally describing all known vibrational–rotational energy levels in the ground electronic state. The standard deviation of the fit is 0.0015 cm⁻¹. The eigenfunctions of this effective Hamiltonian have then been used in fittings of parameters of an effective dipole-moment operator to more than 600 observed line intensities of the cold and hot bands covering the ν₂ and 3ν₂ regions. The standard deviations of the fits are 3.2 and 12.0% for these regions, respectively. The quality of the fittings and the extrapolation properties of the fitted parameters are discussed. A comparison of calculated line parameters with those provided by the HITRAN database is given. Finally, the first observations of the 2ν₁ + 5ν₃ and ν₁ + 2ν₂ + 5ν₃ absorption bands by means of photoacoustic spectroscopy (PAS) is presented. The deviations of predicted line positions from observed ones is found to be less than 0.1 cm⁻¹, and most of them lie within the experimental accuracy (0.007 cm⁻¹) once the observed line positions are included in the global fit.     

An ab initio anharmonic force field of SiHCI3

An ab initio quartic force field of SiHCl₃ is derived using the second-order M?ller-Plesset perturbation theory and Dunning's correlation consistent triple-zeta basis set. After a minor empirical adjustment for the six diagonal quadratic force constants, most fundamentals of SiHCl₃ and SiDCl₃ agree with the experimental values within 1 cm^?1. Additionally the observed overtones, combinations and hot band centres can also be well reproduced. Vibrational analysis based on the second-order perturbation theory is carried out with the calculated force constants. Two sets of spectroscopic constants are predicted for ²⁸SiH³⁵Cl₃ and ²⁸SiD³⁵Cl₃, respectively.     

Thermal decay of stable colour centres in Gd3Ga5O12 crystals

This work is devoted to an analysis of thermal decay processes of the stable colour centres (CC) created in gadolinium gallium garnet (GGG) Gd₃Ga₅O₁₂, crystals under irradiation by gamma-quanta (E=1.25 MeV, D=10⁶ Gy). An analysis of the model of CC accumulation under irradiation as well as an isochronous heating model is presented. The decay activation energy (Δ E) for O^? and F centres in GGG crystals is calculated in accordance with this model.     

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     

First-principles study of bulk and surface oxygen vacancies in SrTiO<Subscript>3</Subscript> crystal

The structural and electronic properties of the neutral and positively charged oxygen vacancies (F and F⁺ centres) in the bulk and on the (001) surfaces of SrTiO₃ crystal are examined within the hybrid Hartree-Fock and density functional theory (HF-DFT) method based upon the linear combination of atomic orbital (LCAO) approach. A comparison of the formation energy for surface and bulk defects indicates a perceptible propensity for the segregation of neutral and charged vacancies to both SrO and TiO₂ surface terminations with a preference in the latter case which is important for interpretation of space charge effects at ceramic interfaces. It is found that the vacancies reveal more shallow energy levels in the band gap on surfaces rather than in the bulk, in particular, on the TiO₂ surface. The charged F⁺ centre has significantly deeper energy levels both in bulk and on the surfaces, as compared with the neutral F centre.     

Approximate radiative properties of methane at high temperature

Band model parameters for high-temperature methane have been generated up to 2000 K from an extended spectroscopic database. Part of the spectroscopic data are issued from calculations made in the framework of the effective Hamiltonian approach. These data have been completed by a statistical extrapolation. The calculations of global radiative properties such as band absorbtances and total emissivities are in good agreement with the available experimental data showing that the contribution of the hot bands is correctly taken into account. Finally, the degree of correlation between CH₄, CO₂ and H₂O spectra in typical conditions of combustion applications is discussed. Band model parameters are available upon request.