Density-Functional Theory Calculations of Normal Modes and Raman Intensities for Tetraazaporphin

The structure, harmonic frequencies, and nonresonance Raman intensities for porphin, tetraazaporphin (TAP), and three of its isotopomers are calculated by the density-functional theory of B3LYP/6-31G(d). Scaling of force constants for porphin in nonredundant natural coordinates is performed. The scaling factors obtained were used to predict the force field and normal modes of TAP and three of its isotopomers. Two alternative methods are used to carry out reliable assignment of the TAP frequencies: wavenumber-linear scaling method and frequency-shift method. There is good agreement between the frequencies predicted within the framework of the three methods used. The conservativeness of the out-of-plane B _2g - and B _3g -modes for porphin and TAP is examined. The Raman spectrum for TAP is simulated. A refinement of the assignment of the experimental frequencies for TAP of even symmetry types on the basis of the calculations performed is made.     

Experimental and quantum chemical study of pyrrole self-association through N-H?π hydrogen bonding

An FT-IR study of pyrrole self-association in CCl₄ solutions was carried out. According to the IR measurements, pyrrole forms self-associated dimeric species via N-H?π hydrogen bonding. This was also confirmed by quantum chemical calculations for pyrrole monomer and dimer at B3LYP/6-31++G(d,p) level of theory. A T-shaped minimum was located on B3LYP/6-31++G(d,p) PES of pyrrole dimer characterized with a hydrogen bond of an N-H?π type, with centers-of-mass separation of monomeric units of 4.520 Å, H?π distance of 2.475 Å, the interplanar angle between the two monomeric units being 72.9°. The anharmonic vibrational frequency shift upon dimer formation calculated on the basis of 1D DFT vibrational potentials is in excellent agreement with the experimental data (84 vs. 87 cm⁻¹). Harmonic vibrational analysis predicts somewhat smaller shift (68 cm⁻¹). On the basis of NIR spectroscopic data, anharmonicity constants for the 2ν(N-H) and 2ν(N-H?π) vibrational transitions were calculated. The orientational dynamics of monomeric and self-associated pyrrole species was studied within the framework of the transition dipole moment time correlation function formalism. The period of essentially free rotation in the condensed phase reduces from 0.05 ps for the monomeric pyrrole to 0.02 ps for the proton-donor molecule within the dimer.     

三包层WⅠ和WⅡ型单模光纤波导色散特性的研究

研究了三包层WⅠ和WⅡ型单模光纤的波导色散特性。结果发现在相同条件下，三包层WⅠ和WⅡ型单模光纤零色散点的调节范围比传统的双包层W型单模光纤明显增大。详细分析了几何参量P、Q和光学参量R1、R2对单模传输时的波导色散特性和低次模截止频率的影响。所得的研究结果为获得更为理想的色散补偿、色散平坦光纤及设计新型无源光器件提供了重要的依据。计算波导色散的方法可推广到多包层光纤。     

Comparisons of pharynx, source, formant, and pressure characteristics in operatic and musical theatre singing

Belting, a vocal technique typically cultivated in musical theatre singing, differs timbrally from operatic singing in many interesting respects. The underlying phonatory differences have not been previously investigated in detail. Yet, belting is frequently associated with disturbances of voice function. Articulatory and phonatory characteristics are investigated in a female subject who is a professional singer (co-author JL) trained in both the operatic and belting styles and in an intermediate vocal technique (“mixed”). This article presents data obtained from this subject by video-fiberoptic observation of the pharynx, inverse filtering of airflow, and measurement of subglottal pressure. The results reveal that belting was characterized by very high subglottal pressures and sound levels, and apparently also by a comparatively high degree of glottal adduction. Comparisons with other investigations of related aspects of belting and operatic singing support the assumption that the data obtained from our subject are representative for these vocal techniques.     

Problem of the free oscillations of a capillary bridge

The free oscillations of a capillary bridge whose equilibrium shape is determined by the surface tension forces and the static gravity field are investigated. The values of 25 “lower” levels of the spectrum of natural oscillations of the capillary bridge are found for various control parameters in accordance with the experimental conditions.     

LIGHTWAVE PROPAGATION IN SUBWAVELENGTH HOLES

In this paper we evaluate methods for calculating dispersion relations for waves with wavelengths of the order of hundreds of nanometres propagating in square waveguides with imperfectly conducting walls. The methods considered here are based on those used previously for rectangular dielectric waveguides.     

Inversion of ν(MHal) stretching frequencies in the spectra of dihalosilylenes, -germylenes, -stannylenes,and their complexes with Lewis bases

The vibrational spectra of tetravalent metal halides (M = Si, Ge, Sn) and the corresponding dihalocarbene analogs M^IIHal₂, obtained by the authors, and the relevant published data are compared. The spectra of the M^IIHal₂ species exhibit inversion of the M-Hal stretching frequencies (ν^s(M^IIHal) > ν ^as(M^IIHal)). This can be used for analytical purposes and allows one to distinguish between the spectra of the M^IV and M^II halides. The IR and Raman spectra of the complexes of dihalogermylenes and -stannylenes with triphenylphosphine and 1,4-dioxane also exhibit inversion of the ν(MHal) stretching frequencies. This confirms the conclusion drawn earlier based on the analysis of the geometric parameters and reactivities of the complexes in question that the divalent state of the M atom in these species is retained. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1089–1092, May, 2005.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

EFFECTS OF SOURCE PROPERTIES ON CUTOFF FREQUENCY f_(max)

The cutoff frequency f_(max) of radiation from earthquakes is one of the important parameters for studying the source process. By theoretical analysis and numerical experiments on acceleration Fourier spectrum it is suggested that f_(max) mainly depends on the lower values of slip rise time. This result can be used to explain the observational fact that the greater the earthquake magnitude, the smaller the value of f_(max).     

Influence of the exchange‐correlation functional in all‐electron calculations of the vibrational frequencies of corundum (α‐Al2O3)

The equilibrium structural parameters, high‐ and low‐frequency dielectric tensors, Born effective charges, and Γ‐point vibrational frequencies of bulk Al₂O₃ corundum are calculated by using the periodic, ab initio program CRYSTAL, which adopts an all‐electron Gaussian‐type basis set. The effect of basis set and the performance of three different functionals, i.e., LDA, PW91, and B3LYP, are discussed. The mean absolute deviation from the measured frequencies is as small as 7 cm^?1 for both the LDA and B3LYP functionals, indicating that these functionals perform extremely well in this case. The mean absolute deviation increases to 18 cm^?1 when the PW91 functional is used. All three functionals reproduce the equilibrium geometry of corundum to a high level of accuracy, with LDA and B3LYP outperforming PW91 slightly. The comparison of the current all‐electron calculations with previous plane‐wave, pseudo‐potential calculations shows an overall similar performance. The results of isotopic substitution for both Al and O are also presented. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006