Electronic Absorption Spectra of 2-Fluoro-4-bromo, 4-Fluoro-2-bromo and 2-Fluoro-5-bromo Toluenes

Abstract

Absorption spectra of 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes have been investigated in the near ultraviolet region in vapour phase. The band systems correspond to allowed transitions with the most intense bands at 2742.09 Å (36458 cm^?1), 2745.96 Å (36406 cm^?1) and 2771.74 Å (36068 cm^?1) identified as 0,0 transitions in 2-Fluoro-4-Bromo, 4-Fluoro-2-Bromo and 2-Fluoro-5-Bromo Toluenes respectively. The bands in 4-Fluoro-2-Bromo Toluene have been analysed in terms of the ground state fundamental 208 cm^?1 and excited state fundamentals 244, 611, 855 and 1211 cm^?1 and the bands in 2-Fluoro-4-Bromo and 2-Fluoro-5-Bromo Toluenes are explained in terms of the upper state fundamentals 716, 987 and 1230 cm^?1 and 722, 886 and 2130 cm^?1 respectively.     

Magnetic Circular Dichroism Spectra of p-Disubstituted Benzenes Possessing Both Electron-Donating and Accepting Groups

Abstract

The magnetic circular dichroism (MCD) and absorption spectra of some p-disubstituted benzenes possessing both electron-donating and accepting groups were measured. The electronic spectra of the above compounds are characterized by the appearance of two absorption bands, one of which appears at 25000–40000 cm^?1 region with large intensity, and another at 40000–50000 cm^?1 region with rather small intensity. These absorption bands, especially the latter one, have been investigated by means of the MCD spectra and molecular orbital calculations based on the Pariser-Parr-Pople method.     

Vibrational Spectra of Benzylidene Aniline,O-Hydroxybenzylidene O-Hydroxyaniline and its Complexes with Cu(II) and NI(II) Metal Ions

Abstract

The FTIR and FT Raman spectra of benzylidene aniline, and o-hydroxybenzylidene o-hydroxyaniline compounds in the solid state in the wavenumber (1800-200 cm^?1) are recorded. An assignment for nearly all fundamentals are proposed. Comparison of the spectra of trans stilbene and benzylidene aniline reveals that v N-Ph stretch for the latter compound is situated at 1368 cm^?1 in the IR spectra with medium intensity. for o-hydroxybenzylidene o-hydroxyaniline, the stretching modes v N-Ph, and v C-Ph are observed at 1356 and 1226 cm^?1 respectively. the two v O-Ph are observed as intense bands in the IR spectra at 1245 and 1278 cm^?1, respectively. the FTIR spectra of the o-hydroxybenzylidene o-hydroxyaniline complexes with Cu(II) and Ni(II) metal ions are also recorded and assigned.     

Silicon negative ion implantation induced vacancy defects in thermally grown SiO2 thin films

ABSTRACT

Thermally grown SiO₂ thin films on a silicon substrate implanted with 100?keV silicon negative ions with fluences varying from 1?×?10¹⁵ to 2?×?10¹⁷ ions cm^?2 have been investigated using Electron spin resonance, Fourier transforms infrared and Photoluminescence techniques. ESR studies revealed the presence of non-bridging oxygen hole centers, E′-centers and P_b-centers at g-values 2.0087, 2.0052 and 2.0010, respectively. These vacancy defects were found to increase with respect to ion fluence. FTIR spectra showed rocking vibration mode, stretching mode, bending vibration mode, and asymmetrical stretching absorption bands at 460, 614, 800 and 1080?cm^?1, respectively. The concentrations of Si–O and Si–Si bonds estimated from the absorption spectra were found to vary between 11.95?×?10²¹ cm^?3 and 5.20?×?10²¹ cm^?3 and between 5.90?×?10²¹ cm^?3 and 3.90?×?10²¹ cm^?3, respectively with an increase in the ion fluence. PL studies revealed the presence of vacancies related to non-bridging oxygen hole centers, which caused the light emission at a wavelength of 720?nm.     

Infrared Spectra of Morfolonium (mpH)2Mo2Cl6(H20)2(I),(mpH)2Mo2ClxBr6-x(H2O)2(II)/ (mpH)2Mo2Br6(H2O)2(III) and the Pyridinium (PyH)2Mo2I6(H2O)2(IV)Hexahalo-di(aquo): dimolybdate(II) Complexes,Containing Quadruple Metal-Metal Bounds

Abstract

The electronic (800–400 nm), infrared (4000–200,400–20 cm^?1), ordinary Raman (400–200 cm^?1) spectra of morpholinium and the pyridium hexahalo-di(aquo) dimolybdate(II) complexes, containing quadruple metal-metal bonds were investigated. The electronic spectra of the solid compounds at various temperatures (25,100 and 300K) demonstrate intense and structured bands in the visible region (510–582 nm) attributed to the expected δ→δ? transitions.

From the infrared and Raman spectra, the skeletal stretching modes in these complexes have been localized, and the charectenstic bands of these ions were observed in the expected regions.

Finally, the ionic interections were relatively weak, but the existance of phenomena was perceptible and the result was obtained in agreement with X-ray data.     

3-Naphthyl-4-Quinazolone Infrared and Nuclear Magnetic Resonance Band Assignments

Abstract

The ir and nmr spectra of 24 3-naphthyl-4-quinazolones were examined. There are three principal ir bands in the 1500 and 1705 cm^?1 region of the spectra. The first at 1685–1705 cm^?1 is assigned to the tertiary amide carbonyl (ArCONR₂), the second at 1593–1645 cm^?1 to the anil chromophore (ArN=C-N) and the third to the naphthalene ring at 1600 cm^?1. The nmr band assignments are straight forward.     

New Identification Bands in the Infrared Spectra Of 1- and 2-Substituted Benzotriazoles

Abstract

Some new identification bands characteristic of 1- and 2-substituted benzotriazole derivatives have been found in their infrared spectra. The skeletal in- plane rings vibration near 1490 cm^?1 and some bands in the 795-760 cm^?1 region have been typical for 1-substituted compounds whereas the vibrations at 875-820 cm^?1 have been observed as characteristic of a quinoid system of 2-substituted benzotriazoles. New characteristic bards examination allows to identify better both isnmers.     

Molecular Dynamics simulations of borate glasses

Abstract

The results of Molecular Dynamics simulations of borate glass (B₂O₃) using three-particle interactions are presented. These calculations yield a glass consisting of randomly connected BO₃ triangles. Infrared and Raman spectra have been calculated and compared with experimental spectra. The calculated infrared spectra show two main bands, one at 650 cm^?1 and one at 1250 cm^?1, in agreement with experiment. The Raman spectra reproduce the experimental peak at 805 cm^?1 but the peak width is a factor of ten too large. Apparently, the simulated glasses have less short range order than the laboratory glasses.     

Pure Rotational Raman Spectra of Vapor Phase Methanols

Abstract

The rotational Raman spectra of four vapor phase isotopic methanols, CH₃OH, CH₃OD, CD₃OH and CD₃OD, have been reported for the first time in the wavenumber regions from 5 to 100–120 cm^?1. The major parts of the spectra consist of bands equispaced at 3.19, 3.04, 2.56 and 2.46 cm^?1 intervals, respectively, and have been interpreted as the pure rotational S-branch transitions.     

Manganese centers with various valency in alkali halides

Abstract

Optical absorption bands and epr spectra of NaCl: Mn⁺⁺ X-irradiated at liquid nitrogen and room temperature are studied. Manganese epr spectra are divided into three classes, based on the value of hyperfme splitting constants. It is shown that the epr spectra with the hyperhe splitting constants of around 250 × 10-⁴, 80 × 10^?4 and 20 × 10^?4 cm^?1 are caused by Mn⁺, Mn⁺⁺ and Mn⁹, respectively. Formation of several manganese centers by X-irradiation is discussed. It is suggested that optical absorption bands at 410 and 440 nm are caused by Mn^O at the lattice site and that the Mn^O center which gives an epr spectrum with A = 15. 5 × 10^?4 cm^?1 is associated with a Mn⁰ center which is not at a substitutional site.     

Vibrational Assignment of 2-Benzoyl Pyridine and its 18O Labelled Isomer

Abstract

Vibrational spectra of 2-benzoyl pyridine and 2-benzoyl pyridine-¹⁸O have been recorded in the solid and molten state in the infrared (4000–100 cm^?1) and in the Raman (4000–50 cm^?1). Polarized Raman spectra in the molten state have also been measured. The assignment of the vibrational bands is performed using the group vibrational concept, isotopic shifts and polarization features of the normal modes.     

Drift study of the products formed by radiolysis and photolysis of alkaline nitrates

The products of the radiolysis and photolysis of crystalline sodium, potassium, rubidium, cesium nitrates have been investigated by the diffuse reflectance infrared Fourier transform spectroscopy. The bands in the 1260-1220 and 804-809 cm^?1 regions observed after the n -irradiation and photolysis by a light with the wave length 253.7 nm of crystalline alkali nitrates were identified as the vibrational modes of NO^? ₂ x ₃ and x ₂, respectively. The frequency of the x ₃ oscillation of nitrite ions decreases from 1260 cm^?1 up to 1220 cm^?1 with the increase of the atomic weight or polarizability of a cation. The detection limit of the nitrite ions (1 ‐ 10^?7 mol g^?1) for the diffuse reflection method has been determined. The bands observed in KNO₃, RbNO₃ and CsNO₃ spectra in the 947-940 and 722-737 cm^?1 regions appearing only after photolysis are due to stretch oscillations of the peroxide bond O-O and wagging oscillations of the -ON=O group of peroxynitrite accordingly.     

Normal Unenhanced Raman Spectra of CO and CH4 Adsorbed on Cobalt(poly)

Abstract

Normal unenhanced Raman spectra (NURS) of low-polarizability CO molecules were observed for the first time on cobalt at R. T. and residual gas pressure. We assign five bands observed between 2030–2130 cm^?1 to linear chemisorbed CO species, while those observed between 1840–2010 cm^?1 have been ascribed to the 2-fold chemisorbed species. The three bands observed between 1740–1830 cm^?1 we believe are due to the 3-fold species. The corresponding fourteen Co-C stretches were observed and assigned. A model based upon electron backdonation is proposed for each of the three structures. NURS were also observed at R. T. for physisorbed CH₄ and assignments are made to the four frequencies of CH_4.     

IR spectroscopic manifestations of hydration of poly(diphenyl sulfophthalide) during its storage

IR spectroscopy measurements show that films of poly(diphenyl sulfophthalide) (PDSP), a cardo polymer, interact with atmospheric moisture during storage at room conditions. A total of 15 absorption bands were isolated in spectra of PDSP hydrated during storage, which belong to sorbed water and hydrolysis products. A number of absorption bands (within 1500–1800 cm⁻¹ and 980–1100 cm⁻¹) were obtained by subtracting the spectrum of the film after heating from that of the initial hydrated film. At least six individual bands in the region of the O-H bond stretching vibration were isolated by decomposing a broad complex band (3700–2000 cm⁻¹) into Gaussian components. The isolated bands were tentatively assigned based on the available literature data and quantum-chemical calculations of the characteristics of a number of complexes of a diphenyl sulfophthalide model compound with water molecules. The IR spectra and energies of the hydrogen bonds formed were calculated at the B3LYP/6-311G(d, p) level. In particular, the absorption bands at 1010 and 1079 cm⁻¹ were assigned to the symmetric stretching vibrations of the S=O bonds in the −SO₃⁻ anion, the 1062-cm⁻¹ absorption band, to ν(C-OH), and the absorption bands at 3646, 3586, and 3475 cm⁻¹, to complexes of water with sulfophthalide cycles of the polymer. After a long storage, PDSP largely transforms into a polymeric oxonium salt, and its spectrum becomes similar to that of a polymeric salt prepared by alkaline hydrolysis. A general mechanism of the interaction of PDSP with water is proposed, according to which the hydrolysis of the sulfophthalide cycles (SPC) by sorbed water yields new hydrophilic groups, sulfoacid, and hydroxyl groups. A further sorption of water by the sulfoacid results in its ionization and the formation of various hydroxonium forms. Sorption and hydrolysis are reversible processes: water is desorbed and the SPC is recovered when the polymer is heated to 100–150°C, as can be judged from an increase in the intensity of the S=O bond vibrations of the sulfophthalide cycle at 1352 and 1192 cm⁻¹. The possibility of using strongly hydrated PDSP for manufacturing proton-conducting membranes is discussed.     

The Vibrational Spectra of 9-Fluorenone and Some of Its Isotopic Isomers

Abstract

Vibrational spectra of 9-Fluorenone, 9-Fluorenone-¹⁸O and 9-Fluorenone-d₈ have been recorded in the solid state and solutions in the infrared and (4000–100 cm^?1) and in the Raman (4000–50 cm^?1). Differential infrared linear dichroic spectra have also been measured. The assignment of the vibrational bands is performed using the group vibrational concept, isotopic shifts and polarization features of the normal modes.     

Coupling of the Double Bond Stretching Vibration in Divinyl Ethers

Abstract

Examination of the Infrare and Raman spectra of cis, cis-dipropenyl ether (which was produced by isomerization of diallyl ether) has produced evidence for strong vibrational coupling between the two double-bonds. This ether has strong bands it 1655 cm^?1 in the infrared and at 1691 cm^?1 in the Raman. The 1658 cm^?1 band in the Raman is about 10 fold less intense than the strong polarised band. Thus it appears reasonable to associate the strong IR and Raman bands with the asymmetric and symmetric vibrations shown.     

Unusual Bands in the Infrared Spectra of Some Chars

Abstract

When organic materials are charred at low or medium temperatures (up to about 450–500°C), their infrared (IR) spectra show a plethora of bands below about 2000 cm^?1, and there are additional bands in the OH and CH stretching regions, above about 2600 cm^?1. The in-between region, from about 2600 to 200 cm^?1, is quite “empty” (except for an occasional atmospheric CO₂ band caused by instrument imbalance). The reason for this emptiness is, simply, that there are very few species that have fundamentals in that region, as is well known from group frequency tables; and those that do absorb, such as metal hydrides, are quite unlikely to exist in organic precursors. Some overtones or combinations may appear, but these are usually very weak. We have, however, observed some bands in the empty region on several occasions.     

Infrared Spectra of the Square Planar Rhodium(I) Complexes cis-[Rh(CO)2(pyridine) (X)] (X = Cl,Br): Isotopic Labelling Studies and Normal Coordinate Analysis

Abstract

The infrared spectra (4000 - 50 cm^?1) of the square planar rhodium(I) complexes cis-[Rh(CO)₂ (pyridine) (X)] (X = Cl, Br) and their isotopomers with pyridine-d ₅ and ¹³CO have been determined. Assignments are based on earlier studies on pyridine and its complexes and on the shifts in infrared bands which are caused by the isotopic substitutions employed. Normal coordinate analysis following the procedure of Becher and Mattes has been used to confirm the empirical assignments. The two v(RhC) bands are observed near 490 and 450 cm^?1. v(RhN) is found near 210 cm^?1 and v(RhX) occurs at 310 (X = Cl) and 235 (X = Br) cm^?1. At frequencies below 200 cm^?1, the bands are assigned to bending modes in the following sequence: δ (RhN) > δ (CRhC) > δ (RhCl) > γ (RhCl) > γ (RhN).     

Vibrational Assignments of Some Monosubstituted Pyridines

Abstract

The infrared spectra of 2-(ortho) and 4-(para) vinyl- and ethyl-pyridines have been analysed in the region 400–4000 cm^?1 in liquid phase. The bands obtained are discussed assuming the molecules under C_s and C_2v point groups. The group sensitive fundamentals are compared with those of similar molecules reported in the literature.     

Substituent Effects on the Bands Near 1600 cm−1 in The Ir Spectra of Azobenzene and Some Substituted Azobenzenes

Abstract

The mean positions and apparent extinction coefficients of the ring stretching bands near 1600 cm^?1 in the IR spectra of trans azobenzene and some substituted trans azobenzenes are reported. These results are discussed in relation to values reported for substituted benzenes.