Vibrational spectroscopy of trans and cis deuterated formic acid (HCOOD): Anharmonic calculations and experiments in argon and neon matrices

The absorption spectra of trans and cis conformers of deuterated formic acid (HCOOD) isolated in argon and neon matrices are analyzed in the mid-infrared and near-infrared spectral regions (7900-450 cm⁻¹). Vibrational excitation by narrow-band IR radiation is used to convert the lower-energy trans conformer to the higher-energy cis form. A large number of overtone and combination bands are identified. The results of anharmonic vibrational calculations (CC-VSCF) for both conformers are reported and compared to the experimental spectra.     

Vibrational Analysis of 1,2-Dibromopropane and 1,2-Dibromopropane-D6

Abstract

Infrared spectra were obtained for 1,2-dibromopropane-d₆ in the liquid and in the unannealed and annealed solid states. Vibrational assignments were made for the three conformers of 1,2-dibromopropane and the three conformers of 1,2-dibromopropane-d₆ with the aid of normal coordinate calculations. All three possible conformers of CD₂BrCDBrCD₃ were found to be present in the liquid and unannealed solid, but the P_HS_HH conformer was absent in the annealed solid.     

Conformeric fluorescence and phosphorescence of aromatic molecules with a possibility of rotation of chromophoric fragments around single chemical bonds

Absorption, fluorescence and phosphorescence spectra of trans-stilbene,trans-1-phenyl-2- (2-naphthyl)-ethylene, trans-1,2-di(2-naphthyl)-ethylene, trans-1,2-di(1-naphthyl)-ethylene and 1,4-di(2-naphthyl)benzene in liquid and solid solutions are shown to be dependent on the wavelenght of excitation, solvent viscosity and temperature. These effects are explained by the existence of comparatively stable conformers (s-isomers) which are formed due to rotation of aryl fragments around single chemical bonds. Estimated difference in the energies of 0-0 transitions in conformers mounts up to 2000 cm^-1. Conformers with different fluorescence quantum yields were found. Existence of dynamic equilibrium between conformers of diarylethylenes may provide a clue for rationalizing some peculiarities in their photochemical behaviour; it is also suggested that the effects discussed may serve as a tool for determination of the shape and size of free volumes in liquids and solids.     

Structural and Torsional Properties of o-Cresol and o-Cresol-OD as Obtained from Microwave Spectroscopy and ab Initio Calculations

The microwave spectra of o-cresol and of o-cresol-OD were assigned using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 3-40 GHz. Two conformers of o-cresol were measured where the hydroxy group is syn with respect to the methyl group in one case and anti in the other. The transitions of both conformers were split due to internal rotation of the methyl group. For syn-o-cresol we found the rotational constants A=3249.45242(18) MHz, B=2202.02546(18) MHz, C=1323.66277(16) MHz, and the barrier to internal rotation of the methyl group V₃=7.912(46) kJ mol⁻¹. In the case of anti-o-cresol A=3273.80084(18) MHz, B=2196.26747(18) MHz, C=1325.36424(22) MHz, and V₃=4.4256(14) kJ mol⁻¹ was obtained. Moreover we were able to determine the quartic centrifugal distortion constants, the angle between the internal rotor axes, and the inertial a axes, and, for the deuterated species, additionally the deuterium nuclear quadrupole coupling constants.     

Raman scattering from 2H and 3R–NbS2

Raman scattering experiments have been carried out on 2H-NbS₂ crystals and 3R-NbS₂ crystals. The spectra obtained from both compounds have been found to contain all the Raman active modes predicted by group theory. A nearest-neighbour lattice dynamics model has also been used to analyze the spectra and qualitative agreement with the experimental results is obtained. The results are also discussed in terms of the modifications expected in the Raman spectra obtained from different polytypes of the same layered compound. Some discrepancies with previously reported results are found.     

Ab initio absorption spectra of 3-tert-butylcyclohexene

We present an ab initio investigation of the optical properties of 3-tert-butylcyclohexene in both its conformers. The optical spectra, here the photoabsorption cross section, have been obtained within density-functional theory at the independent-particle level, and within time-dependent density-functional theory. The optical spectra of the two conformers show small but visible differences, hence suggesting that optical absorption experiments can discriminate among the two molecular geometries. To cite this article: K. Gaál-Nagy et al., C. R. Physique 10 (2009).     

Conformational Analysis of 1,2-Dichlorobutane

Vibrational spectra have been published and normal coordinate calculations have been made for 1,2-dichlorobutane.^1,2 Those calculations were limited to the three conformers that had all four carbon atoms coplanar. Molecular mechanics calculations have now shown a conformer that was omitted to be the second most abundant conformer. Therefore, normal coordinate calculations have been made for this conformer and molecular mechanics calculations have been made for all possible conformers.     

Vibrational spectroscopy of cis- and trans-formic acid in solid argon

Absorption spectra of cis and trans conformers of formic acid (HCOOH) isolated in solid argon are analyzed in the mid-infrared (4000-) and near-infrared (7800-) regions. The HCOOH absorption spectrum reveals matrix-site splitting for the trapped molecule. Narrowband tunable infrared radiation is used to pump a suitable vibrational transition of the trans conformer in order to promote site-selectively the conversion to the cis conformer and separate the spectral features of each site group. Several anharmonic resonances are identified for both conformers. The results of anharmonic vibrational ab initio calculations (CC-VSCF) for the trans and cis conformers of formic acid are reported and compared with the experimental spectra.     

Millimeter wave spectrum of glycine

We present new investigations of the millimeter wave spectra of the two lowest-energy conformers of glycine (NH₂CH₂COOH). Measurements of these spectra have been carried out between 75 and 260 GHz using the millimeter-wave spectrometer in Kharkov. The new data set involves rotational transitions with J up to 44 and K_a up to 15 for conformer I and transitions with J up to 43 and K_a up to 14 for conformer II. This represents a more than twofold expansion both in the frequency range and J quantum-number range in comparison with previous investigations. The improved sets of spectroscopic parameters obtained for both conformers provide accurate transition frequencies for the key lines necessary for radio astronomy searches for interstellar glycine.     

KMM Auger transitions in atoms having 46 ⩽Z ⩽ 84

The results of investigations of KMM Auger transitions in atoms having 46 ?Z ? 84 are discussed. All experimental data were obtained by studying the spectra of electron irradiation accompanying the decay of radioactive nuclei. Comparison of the experimental data is made with existing calculations of the energies and intensities of KMM transitions. Requirements for an adequate theory of the intensities of these transitions are formulated.     

Acoustic nonlinearity parameter B/A determined by means of thermodynamic method under elevated pressures for alkanediols

The so-called Beyer nonlinearity parameter B/A is calculated for 1,2- and 1,3-propanediol, 1,2-, 1,3-, and 1,4-butanediol, as well as 2-methyl-2,4-pentanediol by means of a thermodynamic method. The calculations are made for temperatures from (293.15 to 318.15) K and pressures up to 100 MPa. The decrease in B/A values with the increasing pressure is observed. In the case of 1,3-butanediol, the results are compared with corresponding literature data. The consistency is very satisfactory. A simple relationship between the internal pressure and B/A nonlinearity parameter has also been studied.     

The resolution obtainable in X-ray photoelectron spectroscopy with unmonochromatized Mg Kα radiation

The resolution obtainable in photoelectron spectra excited with unmonochromatized Mg Kα radiation is discussed and the various contributions to the instrumental resolution function considered; theoretical estimates are given. Experimental results are compared with theory. It is found that the instrumental resolution is 0.64 eV for a pass energy of 50 eV, with a lower limit of 0.57 ± 0.03 eV owing to the width of the exciting Mg Kα_1,2 radiation. However, the measured resolution is not much less than the values quoted for monochromator-equipped spectrometers.     

Laser spectroscopy of the B[17.7]8-X8 and C[19.3]9-X8 transitions of holmium monochloride

Several new transitions of holmium monochloride (HoCl) have been studied at high resolution using laser excitation spectroscopy. Two main transitions, B[17.7]8-X8 and C[19.3]9-X8 have been observed and five bands, 0-0, 0-1, 1-0, 1-1, and 2-1 of the B-X transition and three bands, 0-0, 0-1, and 0-3 of the C-X transition have been obtained at high resolution and rotationally analyzed. Among several low lying states observed in dispersed fluorescence was a strong transition from the C state to a state ∼2140 cm⁻¹ above the ground state. Excitation spectra of this transition have shown that there are apparently two states, ∼6 cm⁻¹ apart. Comparison with ligand field theory calculations are consistent with assigning these states to the excited low lying Ho⁺(4f¹¹6s)Cl⁻ configuration. Several other low lying electronic states have been observed in dispersed fluorescence spectra. Although their assignments could not be established, their energies suggest that they are from the Ho⁺(4f¹⁰6s²)Cl⁻ or Ho⁺(4f¹¹6s)Cl⁻ configurations. Rotational constants have been obtained for the B[17.7]8 and C[19.3]9 states and have been used to speculate on the possible electron configurations for these states.     

Oxygen chemisorbed on Cu(001): The Cu3d−O2p interaction studied by angular-resolved photoemission using synchrotron radiation

Angular-resolved photoemission measurements have been performed on a Cu(001) surface with and without a c(2 × 2) oxygen overlayer in the photon-energy range 40–170 eV. The relative peak positions in spectra obtained from the clean surface at various emission parameters as to direction and energy are well predicted by a simple direct-transition model, with different spectra thus corresponding to specific high-symmetry points in the 3D Brillouin zone. Photoelectron emission from the Cu3d-derived states near some of these high symmetry points, especially those near W and K, are strongly affected by the chemisorption. The results further show an oxygen-induced structure in the d-band region near X not previously observed.     

Laser spectroscopy of the A[16.4]8.5-X7.5, A[16.4]8.5-Y[0.15]8.5, and A[16.4]8.5-Z[0.85]7.5 transitions of dysprosium monochloride

Laser-induced fluorescence spectra have been obtained at low resolution using a laser ablation source and pulsed dye laser, and at high resolution using a Broida oven and cw ring dye laser. Dispersed fluorescence spectra from two different excited states, A[16.4]8.5 and B[15.4]Ω (unknown Ω) (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment) showed transitions to the same four low lying electronic states, X7.5, Y[0.15]8.5, Z[0.85]7.5, and an unassigned state at 970 cm⁻¹. High resolution excitation spectra of the A-X 0-0, A-Y 0-0 and 0-1, and A-Z 0-0 and 0-1 transitions were obtained and a global fit to all the data yielded rotational constants for both ¹⁶²Dy³⁵Cl and ¹⁶⁴Dy³⁵Cl. From the band origins, vibrational frequencies of 291 and 284 cm⁻¹ were obtained for the Y[0.15]8.5 and Z[0.85]7.5 states, respectively, suggesting that these two states originate from the Dy⁺(4f¹⁰6s)Cl⁻ configuration. The ¹⁶²Dy-¹⁶⁴Dy and ³⁵Cl-³⁷Cl isotope effects were studied and both indicated a ground state, X7.5, vibrational frequency of ∼230 cm⁻¹ which was reinforced by the observation, in dispersed fluorescence from the B[15.4] state, of a weak transition to a state 233 cm⁻¹ above the ground state. The observed electronic states and their configurational origin are discussed in terms of ligand field theory predictions.     

Missing-mass spectra observed in π + p → p + X at 25 and 40 GeV/c

Missing-mass spectra were obtained in the reaction π⁻p → p X⁻ at 25 and 40 GeV/c at the Serpukhov Accelerator. At low masses a strong peak at 1.3 and a smaller one near 1.7 GeV are observed. In the mass region above 2 GeV no structure exceeding 3μb/(geV/c² is seen.     

Theoretical study of time-resolved photoemission of graphite near Brillouin zone K and H points

The time-resolved photoemission spectra of graphite near the Brillouin zone K and H points are obtained by the many-body time-dependent approach, where the nonradiative relaxation process of the excited electron by the phonon release is considered. The relaxation of the spectral weight is highly suppressed near the H point compared to the K point. This implies that the effective electron-phonon coupling near the K point is stronger than that near the H point.     

Laser spectroscopy of holmium monosulphide: Electronic, vibrational and rotational structure of the A[14.79]8.5-X8.5, A[14.79]8.5-W[0.25]7.5 and A[14.79]8.5-V[0.98]7.5 transitions

Laser induced fluorescence spectra of HoS have been obtained using a Broida oven and a ring dye laser. Dispersed fluorescence spectra showed transitions from a common upper state, A[14.79]8.5 to the v = 0 and 1 vibrational levels of three low lying states, labelled X8.5, W[0.25]7.5 and V[0.98]7.5 (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment). High resolution excitation spectra were obtained for all six transitions and a rotational analysis yielded the following principal constants, in cm⁻¹, for the X, W and V states, respectively: T₀ = 0, 251.8713(31), 980.6969(37); B_e = 0.121903(42), 0.121729(37), 0.122561(34); ΔG_1/2 = 463.8811(46), 462.9411(45), 461.2084(127). For the A state, T₀ = 14794.6987(28) cm⁻¹ and B₀ = 0.112596(29) cm⁻¹. The three low lying states are shown to arise from the Ho²⁺[4f¹⁰(⁵I₈)6s]S²⁻ configuration in accord with Ligand Field Theory predictions. The atomic origin of each of the three low lying electronic states was determined from the observed resolved hyperfine structure.     

Observation of a γ transition in the Λ4H hypernucleus

The γ spectra induced by stopped K^? mesons in a ⁷Li target were obtained in coincidence with the accompanying charged pions. A thorough analysis of these spectra indicates that the observed 1.09 MeV line can be ascribed to a γ transition in the ⁴_ΛH hypernucleus.     

Vibrational analysis of ethylamines: Trans and gauche forms

Starting from force constant values calculated by an ab initio MO method ($\text{4-31G(N}{}^1\text{)}$), and by adjusting the diagonal elements, a practical force constant matrix (F) has been reached which could explain the observed infrared and Raman spectra (in the frequency range lower than 2000 cm^?1) of the gauche form of the ethylamine CH₃CH₂NH₂ molecule and five isotopic species CH₃¹³CH₂NH₂, CH₃CH₂¹⁵NH₂, CH₃CD₂NH₂, CH₃CH₂ND₂, and CD₃CD₂NH₂. The F matrix for the trans form of ethylamine was constructed by transferring ab initio $\text{4-31G(N}{}^1\text{)}$ values and by revising diagonal elements with conversion factors whose values are equal to the corresponding values of gauche form. A nearly complete set of assignments was achieved of the vibrational bands of ethylamines, observed so far in the spectral range 2000–100 cm^?1. In matrix isolation spectroscopy, two bands assignable to the NH₂ wagging vibrations of gauche and trans forms have been found at 775 and 782 cm^?1, respectively, for CH₃CH₂NH₂. They are at 768 and 774 cm^?1, respectively, for CD₃CD₂NH₂. From the intensity changes of these bands observed on changing the nozzle temperature in the matrix formation, the energy difference ΔE (gauche-trans) of these two conformers has been estimated to be 100 ± 10 cm^?1.