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.     

渐近非对称陀螺分子H122C16O的高温光谱

在直接计算分子配分函数的基础上,将无转动跃迁偶极矩平方近似为一常数,计算了渐近非对称陀螺分子H¹²₂C¹⁶O 100000-000000跃迁在中等温度和高温下的线强度. 计算结果在500K时与HITRAN数据库的结果吻合相当好.在温度高达3000K时与HITRAN数据库的结果仍符合较好,表明分子配分函数和线强度的高温计算是可靠的.在此基础上,进一步计算了渐近非对称陀螺分子H¹²₂C¹⁶O 100000-000000跃迁带在极端高温4000和5000K的线强度并报道其模拟光谱.计算结果对大气分子高温光谱的实验测量和理论研究均有一定的参考价值. 关键词： 高温光谱 渐近非对称陀螺分子 配分函数 甲醛     

Determination of vibrational energy levels and parallel band intensities of 12C16O2 by Direct Numerical Diagonalization

The Direct Numerical Diagonalization (DND) technique has been applied to the principal symmetric species of carbon dioxide. A three-dimensional formulation of the DND method has been implemented as a first step in using the method to calculate properties of simple polyatomic molecules. Recent high-resolution observations of both line positions and intensities have been incorporated into the method to yield new values for the potential function and the dipolar coefficients. The results are compared with the potential functions calculated by earlier DND efforts as well as the contact transformation approach. The results are also discussed in terms of the effects of truncation errors caused by the use of finite matrices to represent the Hamiltonian operator. The resulting eigenvectors have been used to determine a dipole moment function from 21 observed band intensity values. This dipole moment function in turn has generated a large list of band intensity estimates for ¹²C¹⁶O₂ parallel bands which are being used to update the AFGL line parameter compilation. This list represents the first published set of band intensity values derived from a consistent quantum mechanical model for a linear polyatomic molecule.     

Far-infrared absorption intensities of H2O and D2O in C6H6

Far-i.r. absorption intensities have been measured for H₂O and D₂O in C₆H₆ solutions. Beer's law plots were found to be nonlinear. From the plots, the equilibrium constants of dimer formation in benzene were estimated to be 2.4M^-1 and 3.3M^-1 for H₂O and D₂O at 20°C, respectively. Based on Onsager's reaction field and including explicitly the effect of differences in molecular size between solute and solvent molecules, the internal moment of a water molecule and the volume ratio of a molecule to a cavity were estimated from the integrated absorption intensity of a D₂O monomer in C₆H₆ as 1.98 D and 0.7, respectively     

Electro-optical parameters and Raman intensities of CH4, CH3D,CH2D2, CHD3 and CD4

The absolute Raman intensities and the depolarization ratios of the vibrational bands of gaseous CH₄, CH₃D, CH₂D₂, CHD₃ and CD₄ have been computed here using a compact formulation of the bond polarizability theory, in its zero and first-order approximations. The agreement with experimental values taken from the literature is very good for the first-order approximation, although the difference between both approximations is not very large for these molecules. The derivatives of the polarizability with respect to the symmetry coordinates of methane are given with signs that are physically meaningful.     

Surface vibrations and the nature of the adsorption state: C2H2 on Pt(111)

Molecular vibrations of C₂H₂ and C₂D₂ adsorbed on Pt(111) at 140 K and ∼300K have been measured by high resolution electron energy loss spectroscopy. The comparison of C₂H₂ and C₂D₂ spectra allows an unambiguous assignment of the observed losses to the excitation of C−H bending, C−H stretching, and C−C stretching modes of nondissociatively adsorbed acetylene. From the relative intensities of losses the hybridisation state is determined to be nearsp ². The C−C stretching frequency indicates a C−C bond order of ∼1.8.     

Light emission from a-Si:C:O:H films fabricated by C2F6 and O2/C2F6 plasma treating silicone oil liquid

Amorphous Si:C:O:H films were fabricated at low temperature by C₂F₆ and O₂/C₂F₆ plasma treating silicone oil liquid. The a-Si:C:O:H films fabricated by C₂F₆ plasma treatment exhibited white photoluminescence at room temperature, while that by O₂/C₂F₆ plasma treatment exhibited blue photoluminescence. Fourier transformed infrared spectroscopy and Raman spectroscopy studies showed that the sp³ and sp² hybridized carbons, SiC bond, SiO bond and carbon-related defects in a-Si:C:O:H films correlated with photoluminescence. It is suggested that the blue emission at 469 nm was related to the sp³ and sp² hybridized carbons, SiC bond, carbon dangling bonds as well as SiO short chains and small clusters, while the light emitting at 554 nm was related to the carbon-related defects.     

Real-gas properties of n-alkanes, O2, N2, H2O, CO, CO2, and H2 for diesel engine operation conditions

The objective of the research outlined in this paper was to develop the analytical approximations for calculating real-gas properties (p-v-T data, thermodynamic functions: internal energy, enthalpy, and entropy, and specific heats) of vapor-phase n-alkanes from C₁ (methane) to C₁₄ (normal tetradecane), O₂, N₂, H₂O, CO, CO₂, and H₂ within the range of pressure 0.05 MPa ≤ p ≤ 20 MPa and temperature 280 K ≤ T ≤ 3000 K aimed for implementation into computational fluid dynamics (CFD)-codes simulating the operation process in modern Diesel engines. The analytical approximations have been developed based on available literature data and on the new equation of state for moderately dense gases. The approximations reported are rather simple and therefore can be used directly in CFD codes. Approximations for mixing rules are also provided.     

Comparisons of some molecular properties calculated with basis sets of Slater-type orbitals and floating spherical gaussian orbitals for BH3, BH4 -, B2H6, B4H4, C2H2, C2H4, C2H6, CH4, and C3H4

Some one-electron molecular properties are calculated for BH₃, BH₄ ^-, B₂H₆, B₄H₄, CH₄, C₂H₂, C₂H₄, C₂H₆, and C₃H₄. The wave functions used are constructed from minimal basis sets of STO's and FSGO's. The results obtained from the latter wave functions show that the good agreement with the STO values of the molecular energy is not always maintained with one-electron properties.     

Structure and equilibrium optical properties of liquid CS2

Equilibrium optical properties of liquid carbon disulphide (CS₂), i.e. its refractive index, Kerr constant and depolarized light scattering intensity are calculated using two models of optical response of the fluid. The first one, the point polarizability approximation (PPA) assumes that a point dipole, proportional to the total polarizability, is induced in each molecule. The second one, the point atomic polarizability approximation (PAPA) assumes that point dipoles are induced in individual atomic sites.

The symmetry components of the intermolecular pair distribution function needed to calculate optical properties of the fluid are obtained by Monte Carlo computer simulation on a hard triatomic model of CS₂ as well as by two approximate approaches using this same model. The approximations are both based on the use of the site superposition approximation (SSA) for the intermolecular pair distribution function. In the first approach, the SSA pair distribution is obtained using the Monte Carlo site-site functions and in the second using the site-site functions calculated using the reference interaction site model (RISM) equations.

Extensive comparisons are carried out between the Monte Carlo results and the two approximations in order to examine the influence of the SSA and the RISM equations on optical properties of CS₂. We conclude that, while these approximations, especially the SSA, have a substantial effect on individual symmetry components of the pair distribution, they predict measurable optical properties with satisfactory accuracy.     

Geometry of C2N2 + and HCN+ from low-energy photoelectron spectroscopy

Quantitative Franck-Condon calculations are applied to the first two band systems of the low energy photoelectron spectrum of dicyanogen (C₂N₂) and to the first band system of hydrogen cyanide. Estimates are made of the bond length changes from the ground electronic state of the molecule to various states of C₂N₂ ⁺ and to the ground state of HCN⁺. These changes are consistent with expectations based on simple molecular orbital theory.

It is shown that there is sufficient intensity in the perturbed first system of HCN, and also that of DCN, to account for an overlapping second system due to the removal of an electron from the 5σ orbital.     

Temperature Dependence of Integrated Intensities of Vibrational Bands in M2GeF6 IR-Absorption Spectra

The paper presents experimental results of studies on the temperature dependence of integrated intensities of vibrational bands corresponding to ₃(GeF ₆) in M₂GeF₆ IR-spectra. It is shown that unlike Na₂GeF₆, Rb₂GaF₆, and Cs₂GeF₆, where the dependence of intensity on temperature is monotonous, in the case of K₂GeF₆ there exist anomalous temperature ranges of 220-240 and 150-170 K, where the intensity of a band, corresponding to ₃(GeF^2- ₆) changes abruptly. The study of heat evaluation, heat capacity, unit cell parameters, and intensities of selective reflexes in K₂GeF₆ X-ray diffraction patterns indicates the presence in this compound, as distinguished from others in the seris considerod, of phase transitions of the first order. On the basis of IB, ¹⁹F NNR, X-rat and calorimetric data, a possible mechanism of polymorphic transformation is discussed.     

Optical,structural characterization and dielectric relaxation of [C2H5NH3]2ZnCl4 compound

ABSTRACT

The new organic-inorganic compound [C₂H₅NH₃]₂ZnCl₄ has been grown by the slow evaporation at room temperature. The zero-dimensional (0-D) structure for this compound was determined by the single X-ray diffraction. It crystallizes at room temperature in the non-centrosymmetric space group Pna2₁ and consists of ethylammonium cations [C₂H₅NH₃]⁺ and [ZnCl₄]^2? tetrahedra anions. That is interconnected by means of hydrogen bonding contacts N-H···Cl. The molecular geometry and vibrational frequencies of [ZnCl₄]^2? and [C₂H₅NH₃]⁺ in the ground state was calculated using density functional method (B3LYP) with 6–31G(d) and 6–311G (d,p) basis set. The optimized geometric bond lengths and bond angles, obtained by using B3LYP/6–311G (d,p), show the best agreement with the experimental data. The optical absorbance was measured in order to deduce the absorption coefficient α, optical band gap E_g. The optical band gap is determined by extrapolating the plotted graph of (αhυ)^1/2 vs. (hυ). The large value of indirect optical band gap energy indicates the insulating nature of this material. Moreover, the extinction coefficient, refractive index and the dielectric permittivity of [C₂H₅NH₃]₂ZnCl₄ compound were calculated and the results are discussed. The evolution of the dielectric loss as a function of frequency revealed a distribution of relaxation times, probably ascribed to the reorientational dynamics of alkyl chains in this compound, and then analyzed with the Cole–Cole formalism.     

High-accuracy calculations of dipole, quadrupole, and octupole electric dynamic polarizabilities and van der Waals coefficients C 6, C 8, and C 10 for alkaline-earth dimers

The static and dynamic electric dipole, quadrupole, and octupole polarizabilities of the alkaline-earth atoms (beryllium, magnesium, calcium, strontium, and barium) in the ground state were calculated. The dynamic polarizabilities obtained were used to calculate the van der Waals coefficients C ₆, C ₈, and C ₁₀ of alkaline-earth metal dimers for the interaction of two like atoms in the ground state. The results are compared with other theoretical and experimental data.     

Structural and vibrational properties of Ca2FeH6 and Sr2RuH6

The structural and vibrational properties of the isostructural compounds Ca₂FeH₆ and Sr₂RuH₆ are determined by periodic DFT calculations and compared with their previously published experimental crystal structures as well as new experimental vibrational data. The analysis of the vibrational data is extended to the whole series of alkaline-earth iron and ruthenium hydrides A₂TH₆ (A=Mg, Ca, Sr; T=Fe, Ru) in order to identify correlations between selected frequencies and the T-H bond length. The bulk moduli of Ca₂FeH₆ and Sr₂RuH₆ have also been determined within DFT. Their calculated values prove to compare well with the experimental values reported for Mg₂FeH₆ and several other compounds of this structure.     

Ab initio prediction of the infrared absorption spectrum of the C2Br radical

The first three electronic states of the C₂Br radical, correlating at linear geometries with ²Σ⁺ and ²Π states, have been studied ab initio, using Multi Reference Configuration Interaction techniques. The electronic ground state is found to have a bent equilibrium geometry, RCC=1.2621Å, R _CBr=1.7967Å, ∠ CCBr=156.1°, with a very low barrier to linearity. Similarly to the valence isoelectronic radicals C₂F and C₂Cl, this anomalous behaviour is attributed to a strong three-state non-adiabatic electronic interaction. The Σ ,Π_1/2,Π_3/2 vibronic energy levels and their absolute infrared absorption intensities at a temperature of 5 K have been calculated for the ¹² C¹² C⁷⁹Br isotopomer, to an upper limit of 2000 cm^?1, using ab initio diabatic potential energy and dipole moment surfaces and a recently developed variational method.     

An AB Initio Correlated Computation of Vibrations in the CIONO2 Molecule

Abstract

ClONO₂ is treated ab initio by the second order M?ller-Plesset perturbation approach with the 6-31G? basis set. The minimum-energy structure is planar (C_s symmetry) while in the activated complex for internal rotation around the NO bond the Cl atom exhibits torsion by 90° but the structure has the C_s symmetry, too. For both structures harmonic vibrational frequencies and IR intensities are calculated. The agreement with available observed data from matrix isolation is very good. The MP₂ frequencies are mostly somewhat lower comparing to related SCF values. The energetics is also evaluated in the MP4 fourth order perturbation treatment. The best value found for the barrier of internal rotation is 31 kJ/mol, i.e. significantly low.     

Density functional study of the polymorphism of Cs2C2 and Rb2C2

By density functional theory-based calculations it is shown that in the athermal limit the orthorhombic polymorph of Cs₂C₂ is more stable by ≈7 kJ/mol with respect to the hexagonal modification, while the energy difference between the corresponding two Rb₂C₂-polymorphs is about 4 kJ/mol. The calculations do not corroborate the experimental finding of unusually long and short C-C bond lengths in Cs₂C₂ at low temperatures. This theoretical result is supported by calculations on monomeric LiCCH, where DFT calculations give all bond lengths within 1%.     

N2第二正带系发射光谱的理论计算及实验研究

本文利用分子光谱理论系统的计算和分析N₂第二正带系(C³∏_u→B³∏_g)的发射光谱, 以研究光谱强度的分布规律与不同温度条件和气体条件的关系. 基于N₂的三重态能级结构特性, 重点计算和讨论了发射光谱的概个重要参数: 通过求解高、低电子态的哈密顿矩阵得到了振转能级特性; 利用r质心近似法求取了能级间跃迁的电偶极矩函数和爱因斯坦跃迁概率; 进而计算了不同振动和转动温度条件下谱线的强度分布. 进行了N₂和Ar的混合放电实验, 利用实验光谱数据同理论结果进行拟合分析, 确定了N₂分子的振动温度和转动温度分别约为4300 K和800 K. 另外由于潘宁离化效应, N₂浓度减小时谱线强度呈现先增强后减弱的趋势. 实验结果很好的验证了N₂第二正带系光谱理论计算的正确性.     

Order parameter anisotropy of MgB2 using specific heat jump of layered superconductors

The recently obtained analytical result [1] for renormalization of the jump of the heat capacity (C _S–C _N)/C_N by anisotropy of the order parameter is applied to the layered superconductors. The graph of (C _S–C _N)/C _N vs. the anisotropy of the order parameter allows a direct determination of the gap anisotropy in MgB₂ using available experimental data