Interpretation of vibrational IR spectrum of uracil using anharmonic calculation of frequencies and intensities in second-order perturbation theory

The anharmonic frequencies of fundamental vibrations, overtones, and combination vibrations, as well as the intensities of absorption bands in the IR spectrum of uracil, are calculated. The anharmonic quartic force field and the third-order dipole moment surface calculated by the DFT quantum-mechanical method (B3LYP/6-31+G(d,p)) are taken as the initial parameters. The anharmonic frequencies and intensities of vibrations are determined using the second-order perturbation theory in the form of contact transformations. Multiple Fermi resonances and polyads are determined by the diagonalization of a small interaction matrix of vibrations of different types (fundamental, combination, and overtone frequencies). The total experimental IR spectrum of matrix-isolated uracil is interpreted. It is shown that the used method of calculating anharmonic frequencies and intensities can form a basis for anharmonic calculations of vibrations of moderate molecules.     

Calculation of the Band Intensities of the IR Spectra of Oriented Polymers

An attempt has been made to extend the theory of IR spectra of polymers to oriented polymers. Formulas for the absorption-band intensities in polarization IR spectra of oriented polymers reflecting the dependence of the polarized absorption-band intensity on the structural and orientation characteristics of polymers have been obtained. These formulas permit calculating the intensity of polarized absorption bands at different degrees of orientation of the polymer.     

Spectroscopic Analysis of Organophosphorus Pesticides Using Colorimetric Reactions

The UV-Vis and infrared (IR) absorption spectra of organophosphorus (OP) pesticides have been studied. A correlation in spectra was developed to optimize the OP pesticides in the environments. The spectroscopic (UV-Vis and IR) spectrum of OP pesticides like methyl parathion, malathion and parathion has been interpreted in detail. A complete calculation of the normal frequencies and absolute intensities of UV-Vis and IR absorption bands are interpreted with the help of corresponding experimental data. In the colorimetric reactions, the bands appear at 2 077, 1 637, 1 455, 1 015, 655 cm-1 for malathion; 2 081, 1 639, 1 316, 1 015, 794, 683 cm-1 for parathion; 2 078, 1 632, 1 032, 794 cm-1 for methyl parathion were used for quantitative or qualitative analysis. All these IR spectra were acquired by averaging 100 scans at a resolution of 4 cm-1. It is determined experimentally in the region 200～450 nm for UV-Vis absorption bands and in the region 400～4 000 cm-1 for IR absorption bands. It is concluded that the mainly optically active groups (P—OH, CO, PO, C—O—C, P—O—C, PS, —OH) present in pesticides which are responsible in change in significant data for quantitative and qualitative analysis. The various optical properties like wavelength, band energy, wave number, and frequency, also are calculated.     

Theoretical analysis of the IR spectrum of methyl-3,4-anhydro-α-D-talohexopyranoside

A detailed interpretation of the IR spectrum of methyl-3,4-anhydro-α-D-talohexopyranoside that is based on complete calculation of normal vibration frequencies and absolute IR absorption band intensities of the molecule and a comparison of the results obtained with the corresponding experimental data is given for the first time. The influence of the epoxy group on the absorption bands characteristic of the pyranose ring has been analyzed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 597–605, September–October, 2008.     

Analysis of glucopyranoside trinitrate IR spectrum

The IR spectrum of 4-O-methyl-2,3,6-tri-O-nitromethyl-β-D-glucopyranoside has been interpreted in detail for the first time based on complete calculation of the normal vibration frequencies and absolute intensities of its IR absorption bands and a comparison of them with the corresponding experimental data. The results indicate that the location of the nitrates in cellulose nitrates can be determined experimentally from separate components of complicated absorption bands in the ranges 1700–1600 and 900–800 cm⁻¹ of the IR spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 43–51, January–February, 2008.     

Interferometric determination of the dispersion of vibrational polarizability and the integrated intensities of fundamental bands of 32, 34SF6 and NF3 molecules

The refractivity of gaseous SF₆ and NH₃ in the region of the intense absorption bands of these compounds was measured by two-beam, two-color interferometry using a He-Ne laser and a CO₂ laser tunable throughout its emission lines. Quantitative data on the profiles of the absorption bands of these gases were also obtained by IR Fourier spectroscopy. By using the joint processing of the results of refractometric and spectral measurements on the basis of the Kramers-Krönig formalism, the dispersion dependences of the vibrational polarizabilities of the given molecules were calculated and the integrated intensities of their fundamental vibrational bands were refined. A table of values of total and vibrational polarizabilities at the emission frequencies of the CO₂ laser was compiled.     

Isotope Effects in the Spectra of Hydrogen-Bonded Complexes. Anharmonic Calculations of Isotopologues of the [F(HF)2]– Complex

Optics and Spectroscopy - The frequencies and intensities for IR absorption bands of symmetric and asymmetric hydrogen-bonded complexes [FL1FL2F]– (L1, L2 = K-meson Ka, proton H, deuteron D,...     

IR and Raman studies of polythiophene prepared by electrochemical polymerization

IR and Raman studies have been carried out for polythiophene prepared by electrochemical polymerization and subsequently treated with aq. NH₄OH solution to neutral film. Four additional strong absorption bands at 1330, 1200, 1100 and 1030 cm^?1 appeared upon doping irrespective of the nature of dopants and their intensities increased with increasing dopant concentration. Polydeuterothiophene obtained by the same method gave similar additional strong bands shifting slightly to lower frequencies. These four intense IR bands did not appear in the Raman spectra of doped polythiophene films. Origin of these IR bands can be attributed to ring stretching of the charged polythiophene chain.     

Calculations of molecular ir spectra in the overtone and combination frequency regions

Frequencies and intensities of fundamental, overtone, and combination absorption bands have been calculated in an anharmonic approximation for substituted benzene and ethene, aldehydes, ketones, and alcohols in the range 400–4000 cm^–1. The calculated values agree well with the experimental data. It is shown that such a calculation allows one to study and predict dependences of the frequencies and intensities of the overtone and combination bands on the substance structure.     

1,1'联萘-2,2'-二胺拉曼和红外光谱的实验和DFT计算研究

实验测量了1,1''-联萘-2,2''-二胺（BINAM）的红外吸收光谱、可见光激发普通拉曼光谱、紫外共振拉曼光谱.用电子密度泛函方法计算了BINAM的基态几何构型、振动频率、普通拉曼和近共振拉曼强度.通过实验和理论计算对比,对所得红外和拉曼提出了详细的指认,并且分析了各振动模式的特征.BINAM的紫外共振拉曼光谱与普通拉曼光谱相比较,发现有若干拉曼谱带出现了选择性共振增强.基于共振拉曼强度分析,讨论了BINAM可能的激发态几何结构的变形.     

Laser spectroscopic study of ozone in the 100←000 band for the SWIFT instrument

A complete spectroscopic study of 15 strong ozone lines in the 1132.5–1134.5 cm^?1 spectral range has been undertaken in the framework of the development of the stratospheric wind interferometer for transport studies (SWIFT), led by the Canadian Space Agency. Measurements have been performed with an interferometrically stabilized tunable diode laser spectrometer. Absolute line positions and intensities have been determined with high accuracy (4×10^?5 cm^?1 and 1–2% respectively). Self- and air-broadening coefficients at 296 K have been obtained with an accuracy of 1%. The air-shifting coefficient and its temperature dependence have also been measured for unblended lines together with the temperature dependence of the air-broadening. Line intensities have been calibrated by simultaneously performed UV absorption measurements at 253.7 nm. Our IR/UV comparison supports a previously reported inconsistency between recommended IR intensities (HITRAN08) and UV absorption cross-sections and indicates that current IR intensities are too small by ～3%.     

Integral intensities of characteristic absorption bands of vinyl esters

The infrared absorption band frequencies and absolute integral intensities for the carbonyl C=O and vinyl C=C group stretching vibrations in vinyl acetate, vinyl benzoate, and six substituted vinyl benzoates have been measured in inert solvents. The asymmetry of the absorption bands for the C=C vibrations of the vinyl group is attributed to Fermi resonance. A correlation between the frequencies and intensities of the bands studied and the Hammett substituent constants has been found.     

Experimental and theoretical study of the IR spectrum of 4-amyloxy-4′-cyanobiphenyl

The IR absorption spectrum of polycrystalline 4-amyloxy-4′-cyanobiphenyl (5OCB) is measured in a KBr pellet over the range 400–4000 cm^?1. The structure of the molecule and the frequencies and intensities of the bands in the spectrum are calculated in the approximation of the B3LYP hybrid density functional with the 6-31G(d) and 6-31+G(d) basis sets. With the method of linear scaling of frequencies, 39 bands of the experimental IR spectrum are assigned. On the basis of calculations for related compounds, the vibrations belonging to the substituents and the biphenyl fragment are ascertained. It is shown that the IR absorption spectra of polycrystalline 4-hydroxypropyl-4′-cyanobiphenyl and 5OCB are almost identical and differ by the occurrence of three bands associated with vibrations localized on the oxyamyl radical.     

Infrared spectroscopy of ICAO taggants

The IR absorption spectra of the ICAO taggants, ethylene glycol dinitrate (EGDN), o-mononitrotoluene (2-NT), p-mononitrotoluene (4-NT) and 2,3-dimethyl-2,3-dinitrobutane (DMDNB) in the vapor phase, are studied at room temperature over a wide frequency range (500–4000 cm^–1). The pre-assignment of the observed vibrational bands was performed. Modern quantum-chemical methods are applied to calculate the equilibrium geometries of these molecules and the frequencies of their fundamental vibrations. For the most intense bands of 2-NT and 4-NT, the absorption cross sections are estimated. Based on analysis of current laser technology, it has been concluded that their use in conjunction with the available spectroscopic data makes it possible to reliably perform local and remote detection and identification of ICAO taggants in an open atmosphere in real time.     

Modeling of IR Spectra of Selectively Substituted Glucopyranoside Nitrates

The frequencies of the normal vibrations of the molecules of 2,6- and 3,6-di-O-nitro-methyl--D-glucopyranosides and 2,3,6-tri-O-nitro-methyl--D-glucopyranoside have been calculated within the valence-force-field approximation in combination with calculation of the absolute intensities of the IR absorption bands of these molecules by the CNDO/2 method. The regularities in the structure of the complex IR absorption bands characteristic for nitro groups formed as a result of selective nitrosubstitution have been explained.     

尿素分子红外光谱与晶体红外吸收截止波长的量子化学研究

应用量子化学从头算方法准确计算了尿素分子的红外光谱,得到分子的振动频率和红外振动强度与实验值相符。在分子红外光谱计算的结果基础上估算了尿素晶体的红外吸收截止波长,其值为１．４０μｍ,与测量的符合得很好。对光学晶体红外透过窗口的研究具有重要意义。     

IR Absorption and Raman spectroscopic study of reentrant-nematic liquid crystalline N-[4-(4-Octyloxy-benzoyloxy) Benzylidene]-4-Cyanoaniline (OBBC)

Abstract

The IR absorption and Raman scattering of OBBC have been investigated in the solid, ReN, SmA and nematic phases. The intensity of the 2229 cm^?1 band assigned to the C[tbnd]N stretching mode decreases with increasing temperature in the reentrant nematic phase; this is attributed to a change in the overlap of the molecules. While the IR bands at 1728 and 841 cm^?1 also show a remarkable temperature dependence, Raman bands do not show significant temperature dependence in the liquid-crystal phases.     

Comparison Between the Induced Changes in the Intensities of Mid and Near Infrared Absorption Bands of Poly[Vinyl Alcohol] Due to Temperature and Solvents

The temperature induced changes in the intensities of the infrared absorption bands of PVA in both MID and NIR regions are presented. The absorption band at 1141cm^-1 is the only band among the bands in the mid region which is markedly affected by temperature. This band is taken as a measure of crystallinity of PVA. PVA shows two phase transitions at 80c⁰ and 120c⁰. The absorbances of the 1940nm in the near region is also temperature sensititve. The temperature dependence of the other bands in either mid or near regions is very weak. The effect of non polar and polar solvents such as n-hexane, carbon tetrachloride, toluene, chloroform, methanol and acetone is discussed. Comparison between the solvent induced changes in the intensities of the bands in mid and near regions is carried out. The data demonstrate that the bands in the near region ( overtone and combinations) are more sensitive to solvents than the bands in the mid regions. The combined effect of temperature and solvents on the intensities of absorption bands of PVA is also studied.     

Multiphonon absorption in InP

IR absorption measurements have been made using a high resolution Fourier-transform spectrometer on crystals of InP in the region of (400–4000)cm^-1 at temperature between 11–300k. Very weak, new absorption bands, their absorption coefficients are of ∼10^-1cm^-1, were observed at 996cm^-1, 965cm^-1, 932cm^-1, 838cm^-1, 776cm^-1, 742cm^-1, 718cm^-1, 590cm^-1, 558cm^-1 and 538cm^-1. The frequencies and temperature dependence of these weak bands indicate that they arise from three-phonon processes and appropriate assignments are given. We observed using IR absorption technique for the first time the boron contamination in LEC(B₂O₃)-CZ InP crystal. The content of boron contamination has been proved to be of ∼10¹⁶cm^-3.     

酚醌类化合物振动基频的计算,归属和讨论

本文对４,５－二羟基１,２－苯醌和２,５－二羟基－１,４－苯醌 的振动基频进行了量化计算和实验测定,应用Ｇａｕｓｓｉａｎ９４和ＭＯＰＡＣ计算相结合的方法,取长补短,归属了其振动光谱,并对两者的差异做了讨论。