Physicochemical Studies on Solid Products of Reactions of Chromyl Chloride and Chromyl Acetate with Alkylaromatics. Part II. Electronic Absorption Spectra

The electronic absorption spectra of some chromium(IV) complexes as the products of chromyl chloride and chromyl acetate reaction with alkylaromatics have been studied in some organic solvents. A detailed computer analysis of the spectra including resolution into component bands as well as calculation of crystal field parameter Dq, Racah's parameter B and Franck-Condon analysis of the vibronically structured charge-transfer O—Cr band have been performed. The solvent effect on the Dq parameter has been established.     

高分辨分子吸收光谱中的波长校准方法

本文提出高分辨分子吸收光谱中，以碘分子谱作为参考标准的波长校准方法，编制了以人机交互方式自动完成波长校准的软件，并应用于16 422-17 896cm^-1可见光波段范围内的N2^ 分子离子的高分辨吸收谱线的波长校准，结果表明其绝对准确度可达0.006cm^-1。     

The Electronic Absorption Spectrum of Hafnium Monochloride

Abstract

Intracavity laser spectroscopy has been applied for investigation of absorption spectrum of HfCl molecule. In the region 560–700 nm 59 bands have been obtained. Rotational structure analysis of 0–0 band indicated that Hund's case (c) of angular moment coupling applied to this molecule. The molecular constants (cm^?1) calculated for upper and ground electronic states are: ω′ = 353.05 cm^?1, ω″ = 379.65 cm^?1, B′=0.21486 cm^?1 B″ = 0.21801 cm^?1.     

A general formula of two-dimensional Franck-Condon integral and the photoelectron spectroscopy of sulfur dioxide

We derived a general formula of Franck-Condon integral for two-dimensional harmonic oscillators () taking into account the Duschinsky effect and applied it to study the photoelectron spectroscopy of SO₂ and . The equilibrium geometries and harmonic vibrational frequencies of , SO₂ and were calculated by using the density functional theory (B3LYP functional) and the coupled cluster singles and doubles with perturbative triples [CCSD(T)] methods with various basis sets up to 6-311+G(3df) and aug-cc-pVTZ. The adiabatic ionization energy and electron affinity were computed by using the CCSD(T) method extrapolated to the complete basis set limit with aug-cc-pVXZ (X = D, T, Q, 5). The simulated photoelectron spectra of both SO₂ and are in accord with the experiment. While the Duschinsky effect plays a role for some weak transitions of SO₂, it can be neglected for . A splitting observed in the experimental photoelectron spectrum of SO₂ is interpreted as contributing from hot bands and combination bands of ν₁ and ν₂, rather than arising from perturbation of a potential barrier as previous researchers proposed. The calculated adiabatic ionization energy and electron affinity are in agreement with the experiment within 0.027 and 0.040 eV, respectively.     

Analysis of the Photoelectron Spectra of Selenium Difluoride and Selenium Dichloride Based on Franck-Condon Factors

The vibrational structure of the photoelectron spectra of selenium difluoride and selenium dichloride have been simulated using the computed Franck-Condon factors in the harmonic oscillator approximation. Spectral simulations have been carried out employing the coupled-cluster singles, doubles, and triples (CCSD(T)) and the Becke three-parameter Lee, Yang, and Parr (B3LYP) values for the ground electronic states of the neutral molecules and the cations selenium difluoride and selenium dichloride, respectively. The Duschinsky rotations among the normal modes of two ground electronic states of species involved in the transition are fully taken into account. The ionization energies obtained for selenium difluoride and selenium dichloride are in reasonable agreement with the experimentally determined values. The spectral simulations of vibrational structures including frequency changes and Duschinsky rotation upon the electronic excitation are in agreement with the experimental results.     

Analysis of the Electronic Vibrational Spectra of Bisanthene by Calculating Normal Modes

At 4.2 K, the quasiline fluorescence and fluorescence-excitation spectra (in the region of the S ₁ S ₀- and S ₂ S ₀ transitions) of bisanthene in n-hexane have been obtained. Using the MO/M8ST method, the calculation of the A _g normal modes in the S ₀, S ₁, and S ₂ electronic states was carried out for the bisanthene molecule; the relative intensities of the transitions in the corresponding vibronic spectra were also calculated. The analysis of the results of calculations and experiment made it possible to draw conclusions on the form of the modes for a number of normal vibrations which are active in the bisanthene vibronic spectra.     

提高大气吸收光谱测量分辨率的新方法

在仪器函数和吸收线型已知的情况下 ,提出了一种非线性拟合退卷积法 ,用于提高气体吸收测量的光谱分辨率。数值模拟和实际应用都表明 :该方法用于室内气体吸收光谱的测量 ,在保持吸收线型不变的情况下 ,可以显著地提高测量的光谱分辨率 ,降低测量噪声。将该方法用于怀特池中模拟大气吸收光谱测量 ,减小了激光线宽对测量结果的影响 ,获得了比较理想的结果。     

Electronic Structure Analysis of USiO4

Uranium is a member of Actinides and plays important role in nuclear science and technology. Electronic and structural investigations of actinide compounds attract major interest in science. The electronic structure and chemical bonding of coffinite USiO4 are investigated by X-ray Absorption Fine Structure spectroscopy （XAFS）. U L3- edge absorption spectrum in USiO4 is compared with U L3-edge spectra in UO2 and UTe due to their different electronic and chemical structures. The study presents XANES （x-ray Absorption Near-Edge Structure） and Extended XAFS （EXAFS） calculations of USiO4 thin films. The full multiple scattering approach has been applied to the calculation of U L3 edge XANES spectra of USiO4, UO2 and UTe, based on different choices of one electron potentials according to Uranium coordinations by using the real space multiple scattering method FEFF 8.2 code.     

Intracavity Electronic Absorption Spectra of MoO and WO Molecules in the Visible Region

Absorption electronic spectra of MoO and WO molecules have been investigated by a intracavity laser technique in the region 550–800 run. New features have been discovered.

As for MoO molecule the rotational analysis of the four bands have been carried out for the first time. Two of these bands were referred to 0–0 transitions arisen from the new (probable triplet) low-lying electronic state, two other bands were referred to transitions arisen from excited components of X⁵II ground state.

As for WO molecule the rotational analysis of 0–0 and 1–0 bands represented A-X and B-X systems have been carried out for the first time. The new band has been discovered which has been referred to new electronic transition.

Molecular constants of new states of both molecules studied have been evaluated.     

The Electronic Absorption Spectra of Binuclear Complexes,[Cu(o-phen) (sal)No3 and [Cu2 (sacch)4(im)4] Crystal

The electronic absorption spectra of crystals of the title componds were recorded and the experimental results were explained quantitatively with the ligand field theory and the radial wave function of bound Cu(II) cation. With these spactra, the range of magnetic interactions between two Cu(II) ions of the title compounds are discussed.     

Thermal Emission Spectrum of the Cobalt Monobromide Molecule

ABSTRACT

The thermal emission spectrum of the CoBr molecule has been photographed for the first time in the spectral region 4200–6000 Å using the high-temperature excitation technique and the 2-meter plane grating spectrograph (PGS-2). The spectrum has been recorded at a reciprocal linear dispersion of 7.3 Å/mm. About 203 red degraded and line-like bands have been recorded, out of which 172 are entirely new. The observed bands have been classified into 31 systems, of which 23 are entirely new. The vibrational analyses have been carried out using band head measurements and the Deslandre table. The ground state of the CoBr molecule is found to be ³Φ with the vibrational constants 318.3, 329.5, and 332.7 cm^?1.     

Solvent Effects on the Electronic Absorption Spectra of Cr(III) Complexes

An influence of the protic solvents on the electronic absorption spectra of chromium (III) complexes was investigated. The high correlation between dielectric constant of solvents and the crystal field parameter Dq as well as between refractive index and oscillator strength of d-d bands were observed. The significance of the ligand - second sphere interactions for studying of solvent effect on complex spectra was stated.     

Polarization of the 274 nm Absorption System of Benzoxazole: A Band Contour Analysis

Abstract

The rotational contour of the origin band of the 274 nm absorption system of benzoxazole vapour has been analyzed and found to be type A. The transition is thus A ¹A (π π ^?) → X ～ ¹A with the transition moment lying close to the long axis of the molecule. Geometrical changes upon excitation are small.     

极紫外波段变栅距光栅刻槽密度变化及光谱分辨能力分析

针对应用于50~150nm波段的变栅距光栅, 采用球面波曝光系统进行优化设计, 分析了不同宽度光栅的刻槽密度变化和光谱分辨能力。理论分析结果表明, 光栅宽度为4mm时, 理论分辨能力高于14000;光栅宽度为10mm时, 理论分辨能力约为9000;光栅宽度为30mm时, 理论分辨能力急剧下降, 约为3000。光栅的宽度越大, 其刻槽弯曲程度就越大, 光栅的光谱分辨能力就越低, 因此球面波曝光系统只适合制作宽度较小的变栅距光栅。     

小波分析与因子分析对吸收光谱去噪性能比较的初步观察

本文就因子分析和小波分析对吸收光谱的去噪能力进行了比较,并考察了此两种技术的不同联合方式的去噪功能,获得了一些初步的结果。     

狭缝中蒸发水分子的红外吸收光谱（英文）

本文研究了硅片狭缝内水分子蒸发过程中的红外光谱吸收特性。通过改变相对于硅片狭缝的红外光偏振方向(水平:偏振方向与硅片狭缝方向平行;垂直:偏振方向与硅片狭缝方向垂直),测量了水分子在3 900～3 600 cm^-1(伸缩振动)和1 800～1 400 cm^-1(弯曲振动)的偏振红外光吸收。结果表明,经硅片间隙蒸发出来的水分子,在3 900～3 600 cm^-1(伸缩振动)和1 800～1 400 cm^-1(弯曲振动)区间,对垂直偏振光吸收较强,对水平偏振光吸收较弱,表明毛细效应导致蒸发的水分子偶极矩方向倾向于硅片狭缝的法线方向。     

Features of Emission and Absorption of Indotricarbocyanine Dyes on Excitation to Higher Electronic States

The manifestation of ion pairs in the absorption and emission of fluorescence by symmetric indotricarbocyanine dyes with the same cation and anions Br, I, and BF₄ in ethanol, methylene chloride, and dichlorobenzene has been investigated. It is shown that the formation of ion pairs on passing to low-polarity solvents, along with the changes in the electronic absorption and emission spectra, manifests itself in the polarization and fluorescence excitation spectra. We were the first to establish that the presence of an equilibrium mixture of contact ion pairs and free ions in solutions has an effect on the position and probabilities of transitions not only for the first but also for higher excited singlet states of the molecules of polymethine dyes. The formation of ion pairs manifests itself more clearly when the spectral-luminescence properties of compounds in the shortwave spectral region are analyzed. It has been established that marked changes arise in the absorption, excitation, emission, and polarization fluorescence spectra, as well as in the lifetime and quantum yield of fluorescence in this spectral region when the solvent is changed.     

Spectroscopic,structural and theoretical studies of 2‐methyl‐4‐nitroaniline (MNA) crystal. Electronic transitions in IR

Polarized FT‐IR, Raman, neutron scattering (IINS), and UV‐Vis‐NIR spectra of 2‐methyl‐4‐nitroaniline (MNA) crystal plates, powder, and solutions were measured in the 10–50 000 cm⁻¹ range. The FT‐IR spectrum of deuterated MNA (DMNA) in KBr pellet, the Raman spectrum of the DMNA powder as well as the EPR spectrum of the MNA powder were also recorded. Complete assignments of bands to normal vibrations have been proposed. Density functional theory (DFT) calculations of wavenumbers and potential energy distribution (PED) have been performed to strengthen the assignments. The analysis of vibrational and electronic spectra has revealed vibronic couplings in MNA molecules in solutions and in crystals. In the polarized FT‐IR spectra of the crystal five unusually large bands are observed in MIR and NIR regions. Their origin is discussed in terms of N H···O, C H···O, C H···H N hydrogen bonds, intermolecular charge transfers, electrostatic interactions, and ion radicals formation in the crystal. The role of a methyl group introduction to 4‐nitroaniline is analyzed. The crystal structure of MNA at the room temperature was re‐investigated. Copyright © 2008 John Wiley & Sons, Ltd.