Calculation of Normal Vibrations of Chlorin by the Method of Density Functionals

Using the DFT/B3LYP method with a 6-31G(d) basis set, the structure, normal vibration frequencies, and the absolute band intensities in the IR spectra of the chlorin molecule and its four symmetric isotopomers have been calculated. Scaling of the force field by the Pulay method in independent and natural coordinates has been carried out. A method for obtaining effective force fields without using experimental data on the fundamental vibration frequencies is proposed. By comparing the vibration modes and constructing special matrices, complete assignment of the fundamental frequencies of porphin and chlorin has been carried out. It has been shown that the majority of porphin macroring vibrations upon pyrrolenine ring hydrogenation are frequency-characteristic and only 12 vibrations change considerably. A frequency correlation with regard for the mode transition between chlorin and all its isotopomers under consideration has been established. Comparative analysis of the force fields of porphin and chlorin in dependent natural coordinates has revealed the unique nonlocal character of the change in force constants of the macroring upon hydrogenation of one pyrrolenine ring. Modeling of the IR spectra of chlorin and its isotopomers has been performed. Assignment and interpretation of the normal vibrations of the molecules under consideration have been carried out.     

Density Functional Theory Calculations of Normal Modes and Infrared Intensities for Tetraazaporphin

By the DFT/B3LYP method with a 6-31G(d) basis set, the structure, normal vibration frequencies, and band intensities in the IR spectra of porphin, tetraazaporphin (TAP), and three of its isotopomers have been calculated. Scaling of the force constants for porphin vibrations in nonredundant natural coordinates has been performed. The obtained scaling factors are used to predict the force field and normal modes of TAP and three of its isotopomers. To carry out a reliable assignment of the TAP frequencies, two alternative methods have been used: a wavenumber-linear scaling method and the frequency-shift method. There is good agreement between the frequencies predicted by the three methods used. The IR absorption spectrum of TAP has been simulated. Assignments of the observed experimental frequencies of TAP of odd symmetry types are suggested.     

Calculation of Plane Vibration Frequencies of the Porphin Molecule

By the DFT/B3LYP method with a 6-31G^** basis set the frequencies of normal vibrations of porphin and its five derivatives have been calculated. Scaling of the force constants for plane vibrations in independent natural coordinates has been carried out. Symmetry coordinates have been introduced and a force field for plane vibrations of the porphin molecule in independent symmetry coordinates has been obtained. Based on an analysis of special matrices and the potential energy distribution, complete matching of the plane vibration frequencies of porphin and its four isotopomers has been performed.     

神东煤镜质组结构模型红外光谱的量子化学计算

为了煤的洁净、高效和高附加值利用,需要从分子水平上了解煤的结构。在文献[5]中,作者以元素分析和13C核磁共振为依据构建了神东煤镜质组(SV)的结构模型,所建模型的13CNMR模拟计算结果能很好的和实验结果比对,为了进一步验证该模型的准确性,以半经验量子化学计算方法VAMP对SV模型结构的红外谱进行了计算。结果显示模拟计算得到的红外谱图与实验谱图相比峰形相似,但整个计算谱明显偏向高波数区域。经过对相关模型化合物的红外谱进行计算,其原因是半经验方法计算所得官能团结构的振动频率均高于实验测试结果。依此对SV结构模型的红外模拟谱进行修正,修正后实验和模拟谱图能很好地吻合,这进一步证实SV结构模型可以真实的反映神东煤镜质组的结构组成特点。     

A study of the molecular structure of DL-serine with the method of low-temperature IR spectroscopy

Use of low-temperature IR spectroscopy in studies of compounds with a developed system of hydrogen bonds such as DL-serine revealed a complete set of vibrational frequencies. The region of manifestation of stretching vibrations of OH groups involved in the formation of strong hydrogen bonds was found. It is shown experimentally that in a crystal some of the molecules of SL-serine exist in the nonionized form. On the basis of analysis of experimental data, frequency ranges of stretching deformation and torsional vibrations of NH ₃ ⁺ , COO⁻, and OH groups were determined more accurately. It is found that in the crystals there exist molecules of DL-serine with different spatial orientation of NH ₃ ⁺ COO⁻, and COH groups. It is shown that conformational diversity of molecular structures is also preserved at T=18 K. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 864–868, November–December, 1998.     

Calculation of the Normal Vibrations of Benzene in the First Singlet Electron-Excited State 1 B 2u

Using the CIS/6-311+G^** method, the normal vibrations of the benzene molecule in the first singlet electron-excited state ¹ B _2u have been calculated. The algorithm of calculation of the force field in dependent coordinates by the method of generalized inversion is described. A method of autoscaling in dependent natural coordinates is suggested. For six groups of natural coordinates scaling factors have been obtained, the use of which has led to agreement between the calculated and experimental frequencies of the vibrations of benzene. The frequencies of the B _1u -symmetry-type vibrations, for which there is no experimental assignment, have been calculated. The problem of selection of the force field in dependent coordinates is discussed.     

Ab initio Calculation of Normal Vibrations of Chlorobenzene in the First Singlet Electron-Excitebd State 1 B 2

An analysis of experimental assignments of the frequencies of normal vibrations of chlorobenzene in the first singlet electron-excited state ¹ B ₂ has been performed with the use of two quantum-mechanical prediction methods — the method of frequency shifts and the method of transfer of scaling factors. Based on the data of this analysis, a new assignment of a number of vibration frequencies has been made. Normal vibrations of the chlorobenzene molecule in the excited state have been calculated by the CIS method with a 6-311 + G ^** basic set. An algorithm of autoscaling in dependent natural coordinates has been proposed. The force field of chlorobenzene has been scaled in dependent natural coordinates. It is shown that the scaling factors of benzene in the electron state ¹ B _2u can be used for calculating the frequencies of normal vibrations of chlorobenzene in the first singlet excited state ¹ B ₂.     

Application of the differential method for determining the composition of a toluene-methyl ethyl ketone mixture by an IR analyzer

A differential method is suggested to analyze two-component systems. It allows a 1.5-fold increase in sensitivity as compared to the ordinary procedure for determination of the composition of toluene-methyl ethyl ketone by an 1R continuous-flow analyzer. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 408–409, May–June, 1999.     

Evaluating the Possibilities of Correcting the Valence–Force Fields Obtained by Quantum–Chemical Methods in Relation to a Nitromethane Molecule

Using a specific numerical example, we consider and discuss a problem of correction of quantum–chemical force fields because of the ambiguous selection of the systems of scaling factors. Additional conditions are suggested that make it possible to narrow noticeably the regions of solutions of the inverse vibrational problem.     

Influence of the Change in Charges on the Atoms of the CNO2 Fragment of Nitrobenzene Derivatives Caused by Substituents on the Frequency of the Antisymmetric Stretching Vibration of the Nitro Group

The dependence of the frequency of the antisymmetric stretching vibration of the nitro group of the para-derivatives of nitrobenzene on the charges on the atoms of the CNO₂ group calculated by the PM3 method has been investigated. It is shown that a change in the position of the absorption band of the antisymmetric stretching vibration of the nitro group of para-derivatives of nitrobenzene, as well as Hammett's constants _p , can be used as a measure of the electronic effect of substituents, that is, of a change in the charges on the atoms of the nitro group.     

Comparison of Theoretical Methods and Basis Sets for ab initio and DFT Calculations of the Structure and Frequencies of Normal Vibrations of Polyatomic Molecules

The dependence of the quality of calculation of the geometric parameters and frequencies of normal vibrations on the choice of the theoretical method and the basis set of Gaussian functions has been investigated within the framework of four approximations (DFT/B3LYP, HF, MP2, MP3), using benzene and s-triazine molecules as an example. It has been shown that the molecular parameters calculated using the basis set without polarization functions within the framework of any of the above theoretical methods agree poorly with the experimental data. It has been concluded that the use of the basis set 6-31G(d) within the framework of these methods with allowance for the electron correlation for calculating the geometric parameters and frequencies of normal vibrations of polyatomic cyclic compounds is most optimum in terms of the relation between the expenditure of time and the quality of the calculation. The coefficients of linear scaling of frequencies have been obtained by the DFT/B3LYP method for 22 basis sets that were tested on porphin, pyrrole, indene, and pyridine molecules. Atypically large errors in determining the frequencies of some benzene and s-triazine vibrations have been obtained in a number of quantum-mechanical calculations with large basis sets. The changes in the force field for these cases have been investigated with the example of the benzene molecule.     

Determination of Microelements in Urine by the Method of Emission Spectrum Analysis with Application of a Fulgurator

The results of investigations of the microelemental composition of urine by the method of emission spectrum analysis are presented. The samples of urine under study were introduced into the arc discharge region by a fulgurator without preliminary preparation of the samples. The content of Pb in the urine samples at a concentration of about 10^–9 g/ml has been determined.     

Energy transfer as a method for investigation of the structure of electrolytes

S. I. Vavilov State Optical Institute, Russia, 199034, St. Peterburg, Birzhevaya Liniya, 12. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 3, pp. 38–42, May–June, 1995.     

Analysis of hydrogen bonds by the IR spectra of thymine and N<Subscript>1</Subscript>,N<Subscript>3</Subscript>-deuterothymine

Calculations of the frequencies and absolute intensities of the IR bands of plane vibrations of thymine and N₁,N₃-deuterothymine in various phase states have been carried out. It has been shown that in the polycrystalline state thymine forms hydrogen bonds C₂=O₈...HN₁ and C₂=O₈...HN₃, and in an aqueous solution the intermolecular interaction is realized by means of the hydrogen bonds O₈...HO and O...HN₁.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 99–105, January–February, 2005.     

Correlated displacement-T2 MRI by means of a Pulsed Field Gradient-Multi Spin Echo Method

A method for correlated displacement-T2 imaging is presented. A Pulsed Field Gradient-Multi Spin Echo (PFG-MSE) sequence is used to record T2 resolved propagators on a voxel-by-voxel basis, making it possible to perform single voxel correlated displacement-T2 analyses. In spatially heterogeneous media the method thus gives access to sub-voxel information about displacement and T2 relaxation. The sequence is demonstrated using a number of flow conducting model systems: a tube with flowing water of variable intrinsic T2's, mixing fluids of different T2's in an "X"-shaped connector, and an intact living plant. PFG-MSE can be applied to yield information about the relation between flow, pore size and exchange behavior, and can aid volume flow quantification by making it possible to correct for T2 relaxation during the displacement labeling period Delta in PFG displacement imaging methods. Correlated displacement-T2 imaging can be of special interest for a number of research subjects, such as the flow of liquids and mixtures of liquids or liquids and solids moving through microscopic conduits of different sizes (e.g., plants, porous media, bioreactors, biomats).     

New Concepts from the Evans Unified Field Theory. Part One: The Evolution of Curvature,Oscillatory Universe Without Singularity,Causal Quantum Mechanics,and General Force and Field Equations

No Heading The Evans field equation is solved to give the equations governing the evolution of scalar curvature R and contracted energy-momentum T. These equations show that R and T are always analytical, oscillatory, functions without singularity and apply to all radiated and matter fields from the sub-atomic to the cosmological level. One of the implications is that all radiated and matter fields are both causal and quantized, contrary to the Heisenberg uncertainty principle. The wave equations governing this quantization are deduced from the Evans field equation. Another is that the universe is oscillatory without singularity, contrary to contemporary opinion based on singularity theorems. The Evans field equation is more fundamental than, and leads to, the Einstein field equation as a particular example, and so modifies and generalizes the contemporary Big Bang model. The general force and conservation equations of radiated and matter fields are deduced systematically from the Evans field equation. These include the field equations of electrodynamics, dark matter, and the unified or hybrid field.     

基于M2因子测量的大气湍流参数的确定方法

基于广义惠更斯-菲涅尔原理以及大气湍流理论,推导出部分相干光束在大气湍流中传输的光束传输M ^{2因子的解析表达式.定量分析了表征大气湍流参数的折射率结构常数 C2_n}和涡旋内尺度 l _{0对 M ^{2因子的影响,并由此提出了一种通过实验测量大气湍流中光束的 M 2因子,进而确定出大气湍流参数的新方法.研究结果表明,由于大气湍流对相干性好的光束影响更为明显,在测量中可采用具有高相干性的基模高斯光束作为测量光源,而测量装 关键词： 2因子')" href="#">光束传输 M 2因子 大气湍流参数 湍流折射率结构常数 湍流涡旋内尺度}}     

Noise spectrum of charge current in a quantum dot system under the irradiation of quantum electromagnetic field

We have investigated the noise spectrum of a quantum dot (QD) coupled to two normal metal leads under the perturbation of a quantum electromagnetic field (QEMF) by nonequilibrium Green?s function method. Current correlation function is determined through making the ensemble average over the lowest SU(1,1)$\mathrm{SU}(1,1)$ coherent state. The fluctuation of QEMF makes important contribution to the noise by imposing an additional term, and quantum feature of the QEMF is transferred to the shot noise. The total noise of our system is composed of three parts: the thermal noise, the quantum field noise, and the shot noise. The quantum field noise is generated from the QEMF, and it dominates the total noise. The shot noise and quantum field noise belong to different types, and they display quite differently. The stair-like and photon-assisted behaviors are obviously exhibited. The enhancement and suppression of noise can be controlled by adjusting the parameters according to its behaviors.