Vibrational and 1H NMR spectra of N-(2-pyridyl)-thioformamide and N-(2-pyridyl)thioacetamide

The Raman and infrared spectra of N-(2-pyridyl) thioformamide and N-(2-pyridyl)-thioacetamide have been measured. The assignment of the bands is aided by the complete normal coordinate treatment for all the vibrations of N-(2-pyridyl)thioformamide and its N-deuterated molecule using a Urey—Bradley force function for the in-plane vibrations and a valence force function for the out of plane vibrations. Variable temperature 1H NMR study of the two pyridylthionamides has also been performed. It is inferred that while N-(2-pyridyl)thioformamide favours a cis —CSNH— group, the other compound favours a trans —CSNH— grouping at ambient temperature.

Infrared Spectra and Conformation of N-Acetylthiourea

Infrared spectra of N-acetylthiourea (ATU) and its N,N,N′-trideuterated compound have been examined in the range 4000–50 cm−1. A complete vibrational assignment with a normal coordinate treatment based on a Urey-Bradley type intramolecular potential function supplemented with valence force function for the out of plane and torsional modes is proposed and the feature of the thioureido vibrations explained. A molecular orbital study by the CNDO/2 method of ATU and its oxygen analog is undertaken and the results are analyzed for a comparative study of the molecular electronic structure and conformation.

Vibrational spectroscopic studies of the ferroelectric LiRbSO4

Lithium rubidium sulphate, LiRbSO4 (LRS), undergoes a sequence of four phase transitions at 166, 185, 202 and 204°C. The phase between 202 and 204°C is incommensurate. Polarized phonon Raman spectra in the frequency region of 50-1200 cm-1 are presented to identify the external and internal vibrational modes at room temperature. The internal mode frequencies of the sulphate ions are presented in the temperature region from -150 to 230°C covering all the phase transitions. The total integrated areas of the 1, 2 and 4 modes show an anomalous increase across the phase transitions. The frequencies of the symmetric stretching (1) and symmetric bending (2) modes do not show any changes at the phase transitions, but the width of the 2 mode shows changes across the phase transitions. A small increase in the linewidth of the 2 mode observed in the incommensurate phase is attributed to the influence of the incommensurate modulation wave. A DSC thermogram showed endothermic peaks during heating at all the phase transitions. The IR spectrum recorded at room temperature showed the expected Au and Bu internal modes.

Vibrational assignments of five-membered heterocyclic compounds. Normal vibrations of oxazolidine-2-one and -2-thione

Infrared spectra of oxazolidine-2-one (Oxo), -2-thione (Oxt) and their N-deuteriated derivatives have been measured over the range 4000-20 cm−1. The fundamental frequencies of these molecules have been assigned on the basis of normal coordinate calculations carried out using a Urey-Bradley potential function supplemented with valence type constants for the out-of-plane modes of the planar skeleton. The results of the vibrational analyses are discussed and correlated with the assignments available for the other related five membered heterocyclic molecules.

Proton NMR and infrared investigations of secondary dithiocarbamate ester: molecular conformation and vibrational assignment of S-methyl N-methyl dithiocarbamate

Rotational isomerism of S-methyl N-methyl dithiocarbamate (MMDTC) has been investigated by means of variable temperature proton NMR and i.r. spectroscopy. The i.r. spectra of MMDTC as neat, solution and at sub-ambient temperatures have been examined. Normal vibrational analysis of all the fundamentals of MMDTC has been carried out, the vibrational assignment has been compared with those of related secondary thioamides to note the consistency in the assignments and to obtain the pattern characteristic of the secondary thioamide vibrations.

Infrared and Raman spectra of 2,4-dithiobiuret and its normal vibrations

The infrared spectra of 2,4-dithiobiuret(DTB), N-deuterated dithiobiuret(DTB-d5) and the laser Raman spectrum of DTB are reported. Normal coordinate treatments of DTB and DTB-d5 have been carried out to aid the assignment of the vibrational frequencies. A trans—cis conformation is favoured for DTB molecule in the solid state.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 mu m

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mu m up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5)(Sigma(+)(u) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

Infra-red spectra of crystalline chloroacetates of Cu, Ca, Sr, Ba and Pb

The infra-red spectra of Cu, Ca, Sr, Ba and Pb chloroacetates were studied in order to investigate the effect of co-ordination on the vibration spectra of the ligand. The shifts of the symmetric and antisymmetric COO− vibrational frequencies indicate a bridged structure as the most probable one for the complexes investigated. No linear relationship between the shifts of the COO− stretching frequencies and E/r (where E is the electron excitation energy and r the ionic radius) was observed. No systematic mass effect on these COO− frequencies also could be established.

Raman spectra of single crystals of adipic and sebacic acids and a study of the hydrogen bond vibrations in carboxylic acid dimers

Raman spectra of single crystals of adipic and sebacic acids have been photographed for the first time using λ 2537 excitation. The spectra have been divided into four regions: (a) internal frequencies; (b) summations and overtones; (c) external vibrations; and (d) low-frequency hydrogen bond oscillations. Tentative correlations have been given for all the internal frequencies and summations and overtones. A series of diffuse weak bands observed in the spectra of both these acids in the not, vert, similar2400–2800 cm−1 have been explained as a superposition of O---H frequencies lowered due to hydrogen bond formation over the summations and overtones of fundamentals mainly in the not, vert, similar1000–1500 cm−1 region. Rotatory type of external oscillations of the two formula units of these molecules in their unit cells have been identified at 76, 99, 118 and 165 cm−1 in adipic acid and 66, 95, 117 and 177 cm−1 in the spectrum of sebacic acid. A brief discussion of the low frequency hydrogen bond vibrations in these acids has been made. Making use of the Lippincott—Schroeder potential and assuming a highly anharmonic potential curve for the hydrogen bond, the vibrational frequencies of the bond have been theoretically evaluated. There is very good agreement between these and the experimental values. The results for adipic acid in cm−1 are: 304 (0 → 1), 270 (1 → 2), 241 (2 → 3), 222 (3 → 4) 201 (4 → 5), 183 (5 → 6). In the case of sebacic acid some of the intermediate and higher transitions are absent in the spectrum recorded by the author. From the above data for adipic acid the dissociation energy of the hydrogen bond was evaluated as 5·9 kcal/mole in fair agreement with the values derived from conventional methods.

Infrared Spectra of Dimethylquinolines in the Gas Phase: Experiment and Theory

Infrared spectra of atmospherically important dimethylquinolines (DMQs), namely 2,4-DMQ, 2,6-DMQ, 2,7-DMQ, and 2,8-DMQ in the gas phase at 80 degrees C were recorded using a long variable path-length cell. DFT calculations were carried out to assign the bands in the experimentally observed spectra at the B3LYP/6-31G* level of theory. The spectral assignments particularly for the C-H stretching modes could not be made unambiguously using calculated anharmonic or scaled harmonic frequencies. To resolve this problem, a scaled force field method of assignment was used. Assignment of fundamental modes was confirmed by potential energy distributions (PEDs) of the normal modes derived by the scaled force fields using a modified version of the UMAT program in the QCPE package. We demonstrate that for large molecules such as the DMQs, the scaling of the force field is more effective in arriving at the correct assignment of the fundamentals for a quantitative vibrational analysis. An error analysis of the mean deviation of the calculated harmonic, anharmonic, and force field fitted frequencies from the observed frequency provides strong evidence for the correctness of the assignment.

Selenoacetamide: Vibrational assignments and normal coordinate analysis

The i.r. spectra of selenoacetamide and its N-deuterated species have been recorded The fundamental frequencies of these compounds have been assigned. Force constants derived for thioacetamide and acetamide were transferred to the present compound and a good agreement with the observed frequencies were achieved. The results are discussed in relation to acetamide and thioacetamide.

Vibrational analysis of boldine hydrochloride using QM/MM approach

A complete vibrational analysis was performed on the molecular structure of boldine hydrochloride using QM/MM method. The equilibrium geometry, harmonic vibrational frequencies and infrared intensities were calculated by QM/MM method with B3LYP/6-31G(d) and universal force field (UFF) combination using ONIOM code. We found the geometry obtained by the QM/MM method to be very accurate, and we can use this rapid method in place of time consuming ab initio methods for large molecules. A detailed interpretation of the infrared spectra of boldine hydrochloride is reported. The scaled theoretical wave numbers are in perfect agreement with the experimental values. The FT-IR spectra of boldine hydrochloride in the region 4000-500 cm(-1) were recorded in CsI (solid phase) and in chloroform with concentration 5 and 10 mg/ml.

Correlations between frequency of infra-red active vibrational modes and copper-oxygen distance in copper oxides. Application to superconductors

The infra-red spectra of a large number of ternary Cu(II) oxides with at least a quasi square-planar coordination of oxygen around the copper ions have been studied. The frequency of the bands with the highest frequency,v max, is found to correlate extremely well with the shortest Cu–O distance.v max increases at an impressive rate of sim20 cm–1 per 0.01 Å when the Cu–O distance becomes less than 1.97 Å, which is the Cu2+–O2– distance in square-planar CuO4 complexes as obtained from empirical ionic radii considerations. The marked sensitivity may be used as a ldquotitrationrdquo procedure not only to assign bands but also to obtain diagnostic information about local coordination in compounds derived, for example, from the YBa2Cu3O7–d structure such as LaCaBaCu3O7–d . The only example where this correlation fails is in the two-layer non-superconducting oxides derived from La2(Ca, Sr)Cu2O6. The significance of this result is discussed. The marked dependence of frequency on the bond-distance is qualitatively examined in terms of an increased electron-phonon coupling to account for the observed tendency of the superconducting transition temperature to go through a maximum as the average basal plane Cu–O distance is decreased.

Vibrational analysis of 1,3-thiazolidine-2-thione and its selenium analogue

The i.r. spectra of 1,3-thiazolidine-2-thione, ?2-selone and their N-deuteriated derivatives have been investigated in the region between 4000 and 20 cm?1. A complete assignment of the fundamental vibrational frequencies has been made based upon the normal coordinate analysis carried out using a simple Urey�Bradley force field supplemented by the valence force constants for the out-of-plane vibrations of the planar molecular skeleton. The proposed assignments are discussed in relation to the group frequencies in structurally related molecules and in terms of the computed potential energy distributions among the symmetry coordinates.