Indole in Argon Matrix: The Near UV Spectra.

Abstract

The near UV absorption, steady-state polarized fluorescence excitation and time–-resolved fluorescence emission spectra of indole in argon matrix are reported. The absorption maxima of the four lowest singlet transitions were identified at 35095 cm^?1(also the S_{1, 0} 0–0 band), 37650 cm^?1 (S_2,0), 47415 cm^?1 (S_3,0), and 51680 cm^?1 (S_4,0). No distinct 0–0 band of the second transition was identified but the linearly polarized, steady-state fluorescence excitation spectrum indicates an onset of weak S_2,0 bands on the blue side of the S_1,0 0–0 peak (35095 + 400 cm^?1). Only one fluorescence emission component, of 4.9±0.2 ns, was obtained by excitation over the S_{1, 0} 0–0 + 565 cm^?1 to S_1,0 0–0 - 245 cm^?1 domain. The reported data strongly suggest the ¹L_b ^?1A₁ and ¹L_a ^?1A₁assignment for the lowest and next lowest transitions, respectively.     

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.     

Spectra-Structure Correlations in 2,2′-Bipyridine Mercury(II) Saccharinate: Comparison With Mercury(II) Saccharinate And Chloromercury(II) Saccharinate∗

Abstract

The infrared spectrum of 1:1 complex of mercury(II) saccharinate with 2,2′-bipyridine, [Hg(C₇H₄NO₃S)₂(C₁₀H₈N₂)], was studied in the CO and SO₂stretching regions. The appearance of the spectrum in the region of the carbonyl stretching modes was correlated with the number of non-equivalent CO groups in the structure. The spectral and structural characteristics of the CO groups in the title compound were compared with the corresponding ones in the mercury(II) saccharinate and chloromercury(II) saccharinate. It was found that the frequency of the CO stretchings in the spectrum of Hg(bpy) (sac)₂ is significantly lower (1630 and 1615 cm^?1) than the frequency of the corresponding modes in the spectra of covalently bonded mercury(II) saccharinate (1705 and 1680 cm^?1) and chloromercury saccharinate (1694 cm^?1). An attempt was also made to assign the bands which are mainly due to the symmetric and the antisymmetric SO₂ stretching vibrations.

     

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.     

A Ketene Intermediate in 3-Cyclopentenone Photolysis : Matrix-Isolation and Gas Phase Experiments

Abstract

Photolysis experiments are performed at λ  230 nm on argon matrix-isolated and on gas phase 3-cyclopentenone ( 1 ); in both cases, a ketene intermediate (KE) is detected (FT-IR spectra : 2121–2126 cm^?1 in argon matrix; 2066–2210 cm^?1 in gas phase). 1,3-butadiene ( 2 ) and carbon monoxide are the reaction products. Two first-order consecutive photochemical processes occur 1 ^k1 > KE ^k2 > 2 + CO with k₁ = 1.7 10–2 s^?1 and k₂ = 2.4 10–2 s^?1.     

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.     

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.     

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.     

Hard mode infrared spectroscopy of CaTiO3—CaFeO2.5 perovskites

Abstract

Powder-absorption infrared (IR) spectra of perovskites CaFe_xTi_1?x O_3?x/2 (0≤x≤1) annealed at different temperatures were investigated at room temperature in the range 135–2000 cm^?1. The spectra change as a function of composition, annealing temperature and structural state (order-disorder of oxygen vacancies). Autocorrelation analysis has been used to determine variations of average line widths of groups of peaks in the primary IR spectra. The band widths increase on increasing Fe content in the region of the structures with disordered oxygen vacancies and they decrease on going through the order-disorder boundary. High degrees of local structural heterogeneity are suggested by the effective line widths of the phases at intermediate compositions. The intensity of bands at ～150 and ～443 cm^?1 decreases with increasing Fe content in the compositional range of the disordered structures. Finally, for every annealing temperature, the frequency of the band at ～600cm^?1 systematically shifts to higher values on increasing Fe content, these values decreasing again for the fully ordered structures.     

Vibrational spectroscopic characterization of the magnesium borate-phosphate mineral lüneburgite

ABSTRACT

Lüneburgite, a rare magnesium borate-phosphate mineral from Mejillones, Chile, has been characterized using Raman and mid-infrared spectroscopy methods. Boron tetrahedra are characterized by sharp Raman band at 877?cm^?1, attributed to the ν₁[BO₄]^5? symmetric stretching mode. The phosphate anion is associated with a distinct band at 1032?cm^?1, attributed to the ν₃[PO₄]^3? antisymmetric stretching mode. The most intensive Raman band at 734?cm^?1 is ascribed to stretching vibrations of bridging oxygen atoms in boron–oxygen–phosphor bridges. Bonds associated with water bending mode and stretching vibration are observed at 1661?cm^?1 (infrared) and in the 3000–3500?cm^?1 region (Raman and infrared spectrum).     

Temperature Effect on the IR Absorption Spectra of Hydrogen Bonded (N[sbnd]…N)+ Homoconjugated Cations

Abstract

The effect of temperature on the absorption spectra from 50 to 3200 cm^?1 of a number of amine semiperchlorates and perchlorates of amines with two basic centres in which the hydrogen bridges (N [sbnd] H…N)⁺ are formed, was investigated. Three broad absorption regions may be distinguished in the spectrum, viz., between 100 and 900 cm^?1, 600 and 1800 cm^?1 and 1700 and 2900 cm^?1. The latter one may be assigned to the stretching vibration ν_S (N [sbnd] H…N).

A shift of this band peak (which is usually a doublet at room temperature for aromatic amines) towards longer wavelengths on decreasing the temperature may be an evidence that the bridge becomes shorter. Simultaneously with these changes, most salts under investigation exhibit a strong increase in low-frequency absorption intensity at about 400–600 cm^?1. It may be suggested that this absorption results from a transition between the split levels of the zero vibrational state.     

Optical and ESR spectra of the C4H radical in rare gas matrices at 4 K

C₄H (butadinyl) was trapped in Ar and Ne matrices at 4 K by the uv photolysis of a mixture of C₄H₂ and the rare gas. CC stretching and CH bending modes have been identified in the ir at 2060 and 735 cm^?1. A band system appearing in the 2500–3000 Å region with (0, 0) at 33 800 cm^?1 has been analyzed and tentatively assigned to a ²Π_r ← X²Σ transition. C₄D: Ar spectra confirm the optical assignments. The ESR spectrum exhibits a proton hyperfine splitting b = A_⊥(H) = 16.5 MHz, at g_⊥ = 2.0004(5). The spin-doubling constant, γ, is estimated to be +0.0006(2) cm^?1.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Electron and electron-phonon effects in the quasi-two-dimensional molecular conductor θ-(BETS)<Subscript>4</Subscript>HgBr<Subscript>4</Subscript>(C<Subscript>6</Subscript>H<Subscript>5</Subscript>Cl): Optical studies at 300–15 K

This paper reports on a study of the polarized reflectance and optical conductivity spectra of the quasi-two-dimensional molecular conductor θ-(BETS)₄HgBr₄(C₆H₅Cl) within the 700–6500-cm^?1 region at 300–15 K and within the 9000–40 000 cm^?1 region at 300 K performed along two principal directions in the crystal plane parallel to the conducting layers of the BETS molecules. The IR spectra obtained at 300 K follow a close-to-Drude behavior, with strong broad features (1200–1400 cm^?1) due to electron-vibrational (vibronic) coupling (VC) superposed on the high Drude background. As the temperature is lowered in the range 180–80 K, in the spectra there appears a Lorentz term with ω_t=2900 cm^?1, as well as three additional VC-induced bands in the 800–1180-cm^?1 region, which disappear as the temperature is decreased further. The results obtained indicate the existence of unstable structural distortions along the two principal directions in the crystal, which are accompanied by the formation of a commensurate charge-density wave.     

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.     

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.     

Raman Spectroscopic Study of the Molybdate Mineral Szenicsite and Comparison with Other Paragenetically Related Molybdate Minerals

Abstract

The molybdate‐bearing mineral szenicsite, Cu₃(MoO₄)(OH)₄, has been studied by Raman and infrared spectroscopy. A comparison of the Raman spectra is made with those of the closely related molybdate‐bearing minerals, wulfenite, powellite, lindgrenite, and iriginite, which show common paragenesis. The Raman spectrum of szenicsite displays an intense, sharp band at 898 cm^?1, attributed to the ν₁ symmetric stretching vibration of the MoO₄ units. The position of this particular band may be compared with the values of 871 cm^?1 for wulfenite and scheelite and 879 cm^?1 for powellite. Two Raman bands are observed at 827 and 801 cm^?1 for szenicsite, which are assigned to the ν₃(E _g ) vibrational mode of the molybdate anion. The two MO₄ ν₂ modes are observed at 349 (B _g ) and 308 cm^?1 (A _g ). The Raman band at 408 cm^?1 for szenicsite is assigned to the ν₄(E _g ) band. The Raman spectra are assigned according to a factor group analysis and are related to the structure of the minerals. The various minerals mentioned have characteristically different Raman spectra.     

Laser excited luminescence spectra of zirconia

Luminescence spectra of ivory zirconia (Zr0₂) excited by an argon-ion laser (19,436–21,839 cm^?1) reveal a complex pattern consisting of both sharp and diffuse peaks in the 16,000–19,000 cm^?1 region. The intensity behavior of these features depends markedly on the excitation frequency. The sharp luminescence peaks of the 18,140–18,600 cm^?1 region are attributed to phonon-mediated de-excitation of excited states of the impuriity-doped ZrO₂ lattice. The more diffuse luminescence bands of the 17,700–18,000cm^?1 region may be associated with the electron traps observed in glow experiments and/or with higher-order phonon processes.     

Subterahertz electrodynamics of (TMTSF)2X (X = ClO4, PF6) salts

The terahertz-subterahertz spectra of the complex permittivity and dynamic conductivity of polycrystalline (TMTSF)₂ClO₄ and (TMTSF)₂PF₆ samples are measured quantitatively. The spectra of (TMTSF)₂ClO₄ have absorption lines at frequencies of 7 and 30 cm^?1. The obtained temperature dependences of the line parameters in the range 5–300 K cast some doubt on the earlier concept of their phonon origin. An excitation is detected at temperatures below 20 K in the frequency range near 30 cm^?1, and its nature is related to the activation of a transverse acoustic phonon caused by the folding of the Brillouin zone due to the ordering of noncentrosymmetrical anions below 20 K. An increase in the carrier relaxation rate is found in this temperature range, which indicates a close relation between the electron and phonon subsystems in (TMTSF)₂ClO₄. Sings of additional low-energy excitations that should manifest themselves at frequencies below 1–2 cm^?1 are detected. (TMTSF)₂PF₆ containing centrosymmetrical anions has no absorption lines in the frequency range 3–20 cm^?1 and the temperature range 5–300 K.     

Comparison of band model and integrated line-by-line synthetic spectra for methane in the 2.3 μm region

The 2.3 μm spectral region of methane can be used to retrieve cloud properties of planetary spectra, provided parameters for the methane spectrum are known. Two standard techniques for calculating absorption spectra in this region are compared here. A Voigt profile Mayer-Goody random band model is applied, using coefficients empirically fitted by Fink et al. to CH₄ spectra recorded with high absorping amounts at 10 cm^?1 resolution. Calculation of the absorption is also done with a line-by-line direct integration method for the same gas conditions using molecular parameters obtained by combining an older unpublished list of observed positions and estimated line strengths (derived from 0.04 cm^?1 resolution data) with quantum assignments from the literature. The molecular parameters have been evaluated for the 4180–4590 cm^?1 region by comparing new laboratory spectra with 0.01 cm^?1 resolution recorded at 296 and 153K with synthetic spectra calculated at the same conditions. The deficiencies of the molecular parameters and random band coefficients for this spectral region of CH₄ are then discussed qualitatively and demonstrated by comparing 10 cm^?1 resolution synthetic spectra calculated by both methods for the same gas conditions at 296, 153, and 55 K.Curves of growth of the total equivalent width are calculated at 296 and 55K for a pathlength of 50 cm and pressures up to 10 atm. Changing the mean line spacing in the band model gives better agreement between the spectra calculated by the two techniques at low gas temperatures. The required multiplier has been determined for the mean line spacing for pressures from 10^?6 to 10^?1 atm at 55, 100, and 150 K.