Far infrared spectrum of silane

The absorption spectrum of SiH₄ from 32 to 400 cm^?1 has revealed two sepasrate bonds,one linear in density and one quadratic.From the linear band,the electric dipole moment produced in the ground vibronic state by centrifugal distortion effects has been estimated to be 9.3 × 10^?6 D in magnitude. From the quadratic band, the molecular octopole moment has been determined to be 3.0 × 10^?34 esu cm³ in magnitude. The simplicity of the techniques used is stressed.     

Far infrared spectrum of stretch-oriented polytetrafluoroethylene

The absorption bands observed at low temperature in the far infrared spectrum of polytetrafluoroethylene have been reanalyzed on an oriented sample in order to establish their dichroism. The results obtained are consistent with the proposed space group P2₁ with two molecular segments per unit cell.     

Far infrared spectrum of orthorhombic sulphur

Absorption spectra in the region 10 - 170 cm^?1 of polycrystalline samples of orthorhombic sulphur have been recorded at 300K and 4.2 K. 5 lattice peaks and the multiplets of the v₈ and v₉ internal modes have been observed. Comparisons with results from recent Raman and neutron scattering experiments and with group theoretical and lattice dynamics calculations give very satisfactory agreement.     

The torsional potential function for n-butane

The energies of four different conformations for n-butane were calculated by the ab initio method using an STO-3G basis set. Fully relaxed molecular geometries obtained from molecular mechanics (MM2) were used. The two energy minima [anti (C_2h), gauche (C₂)] and the two maxima (C₂, C_2v) had the following relative energies: 0.0, 0.88, 3.56, 5.99 kcal/mole. These are approximate Hartree–Fock numbers. It is estimated that inclusion of electron correlation in the calculation would lower the last number to about 5.1 kcal/mole while leaving the first three values essentially unchanged.     

Far infrared spectrum of crystalline carbon disulphide

The far infrared spectrum of crystalline carbon disulphide has been measured at about 1.8 K. Two absorption bands are observed, with maxima at 66.5 and 68.2 cm^?1, respectively, and with nearly equal intensities. They are considered to be due to the two infrared active translational modes expected by lattice dynamics.     

Asymmetric torsional potential function and conformational analysis of furfural by far infrared and Raman spectroscopy

The far i.r. (400-50 cm⁻¹) spectra of gaseous and solid furfural (2-furancarboxaldehyde), c-C₄H₃O (CHO), have been recorded. Additionally, the Raman (3500-20 cm⁻¹) spectra of the gas and liquid have been obtained at variable temperatures and the spectrum of the solid at 25 K. These data have been interpreted on the basis that the molecule exists in two different conformations in the fluid states and that the conformation which has the two oxygen atoms oriented in a trans configuration, OO-trans, is most stable (ΔH ⩽ 1 kcal/mol) in the gas; however, the conformation which has the two oxygen atoms oriented cis, OO-cis, is preferred in the liquid (ΔH = 1.07 ± 0.03 kcal/mol) and is the only rotamer present in the spectra of the solid. The asymmetric torsional fundamental for the OO-trans rotamer has been observed at 146.25 cm⁻¹ in the far i.r. spectrum of the vapor and has five accompanying “hot bands”. The corresponding fundamental for the OO-cis rotamer has been observed at 127.86 cm⁻¹ along with a “hot band” which occurs at 127.46 cm⁻¹. From these data a cosine-based potential function governing internal rotation of the CHO top has been determined and the potential coefficients have values of V₁ = 173 ± 2, V₂ = 3112 ± 20, V₃ = 113 ± 2 and V₄ = −198 ± 6 cm⁻¹. This potential is consistent with an enthalpy difference between the more stable OO-trans and high energy OO-cis conformers being 286 ± 24 cm⁻¹ (818 ± 67 cal/mol) and a trans to cis barrier height of 3255 ± 20 cm⁻¹ (9.31 ± 0.06 kcal/mol). These results are compared to the corresponding quantities obtained previously from microwave spectroscopy and theoretical methods.     

Far infrared spectrum,conformational stability,barriers to internal rotation,vibrational assignment,and ab initio calculations of 2-chloro-3-fluoropropene

The far infrared spectrum (375 to 30 cm^–1) of gaseous 2-chloro-3-fluoropropene, CH₂=C(CH₂F)CI, has been recorded at a resolution of 0.10 cm^–1. The fundamental asymmetric torsional mode is observed at 117.5 cm^–1 with ten excited states falling to low frequency for thes-cis (fluorine atom eclipsing the double bond) conformer. For the higher energy gauche conformer, the asymmetric torsion is estimated to be at 94 cm^–1. From these data the asymmetric torsional potential function has been calculated. The potential function coefficients are calculated to be in cm^–1):V ₁=803±21,V ₂=–94±21,V ₃= 1025±10,V ₄=95±10, andV ₆=2±1, with an enthalpy difference between the more stables-cis and gauche conformera of 550±100 cm^–1 (1.57±0.29 kcal/mol). This function gives values of 1227±50cm^–1(3.51±0.14kcal/mol), 1266±200 cm^–1 (3.62±0.57 kcal/mol), and 665±100 cm^–1 (1.90±0.29 kcal/mol), for thes-cis to gauche, gauche to gauche, and gauche tos-cis barriers, respectively. From the relative intensities of the Raman lines of the gas at 652 cm^–1 (gauche) and 731 cm^–1 (s-cis) as a function temperature, the enthalpy difference is found to be 565±96 cm^–1 (1.62±0.27 kcal/mol). However, the more polar gauche conformer remains in the crystalline solid. The Raman spectrum of the gas has been recorded from 3500 to 70 cm^–1 and, utilizing these data and the previously reported infrared data, a complete vibrational analysis is proposed for both conformers. The conformational stability, barriers to internal rotation, fundamental vibrational frequencies, and structural parameters that have been determined experimentally are compared to those obtained from ab initio Hartree-Fock gradient calculations employing both the 3–21 G^* and 6–31G^* basis sets and to the corresponding quantities for some similar molecules.     

Raman spectrum and potential function of tetrachlorocyclopropene

The laser Raman spectrum of tetrachlorocyclopropene in the liquid and solid phases has been recorded and vibrational assignments are presented. These results together with root mean squared vibrational amplitudes from electron diffraction data have been employed in a normal coordinate analysis in which a 19 parameter potential function is refined. This potential function, originally expressed in terms of compliance constants, is then used to derive the corresponding conventional and relaxed force constants.     

Far infrared spectra of hexachalcogenohypodiphosphates

The far infrared (fir) reflection spectra of the hexachalcogenohypodiphosphates M₂P₂X₆ (M = Mg, Cd, Mn, Fe, Co, Ni, Pb, Sn; X = S, Se) have been studied. $\text{TO}\text{LO}$ splittings are determined from Kramers-Kronig analyses, the splitting is large for the lattice vibration modes of ferroelectric Sn₂P₂S₆ but very small for Ni₂P₂S₆. Measurements with polarized light permit an assignment of the A_2u and E_u modes of the ethane like P₂S₆ units in Mn₂P₂S₆. Factor group analyses were performed for all hitherto described hexachalcogenohypodiphosphates. The fir absorption spectra of the less symmetric compounds Hg₂P₂S₆, Hg₂P₂Se₆, Ca₂P₂S₆, TiP₂S₆, $\text{In}{}_{\mathrm{<mtext>4</mtext><mtext>3</mtext>}}\text{P}{}_2\text{S}{}_6\text{, In}{}_{\mathrm{<mtext>4</mtext><mtext>3</mtext>}}\text{P}{}_2\text{Se}{}_6$, and CuCrP₂S₆ are given.     

The infrared spectrum,light-induced infrared linear dichroism and conformational analysis of phenyl azide in solid nitrogen at 12 K

Phenyl azide (PhN₃) and an isotopic mixture of Ph¹⁴N₃ and Ph¹⁵N¹⁴N¹⁴N were isolated in N₂ matrices at 12 K, and i.r. spectra in the range 4000-400 cm⁻¹ were recorded. Photolysis of matrix-isolated PhN₃ with plane-polarized light generated samples with pronounced linear dichroism in the i.r. spectrum, interpretation of which led to the conclusion that PhN₃ most probably adopts a planar or nearly planar conformation in these conditions. Both the ¹⁵N-shifts and the observed pattern of i.r. dichroism confirm previous assignments made for the liquid-phase Raman spectrum of PhN₃.     

Far infrared spectra, conformational equilibria, vibrational assignments, ab initio calculations and structural parameters for 2-bromoethanol

The far infrared spectrum from 370 to 50 cm⁻¹ of gaseous 2-bromoethanol, BrCH₂CH₂OH, was recorded at a resolution of 0.10 cm⁻¹. The fundamental O–H torsion of the more stable gauche (Gg′) conformer, where the capital G refers to internal rotation around the C–C bond and the lower case g to the internal rotation around the C–O bond, was observed as a series of Q-branch transitions beginning at 340 cm⁻¹. The corresponding O–H torsional modes were observed for two of the other high energy conformers, Tg (285 cm⁻¹) and Tt (234 cm⁻¹). The heavy atom asymmetric torsion (rotation around C–C bond) for the Gg′ conformer has been observed at 140 cm⁻¹. Variable temperature (−63 to −100°C) studies of the infrared spectra (4000–400 cm⁻¹) of the sample dissolved in liquid xenon have been recorded. From these data the enthalpy differences have been determined to be 411±40 cm⁻¹ (4.92±0.48 kJ/mol) for the Gg′/Tt and 315±40 cm⁻¹ (3.76±0.48 kJ/mol) for the Gg′/Tg, with the Gg′ conformer the most stable form. Additionally, the infrared spectrum of the gas, and Raman spectrum of the liquid phase are reported. The structural parameters, conformational stabilities, barriers to internal rotation and fundamental frequencies have been obtained from ab initio calculations utilizing different basis sets at the restricted Hartree–Fock or with full electron correlation by the perturbation method to second order. The theoretical results are compared to the experimental results when appropriate. Combining the ab initio calculations with the microwave rotational constants, r₀ adjusted parameters have been obtained for the three 2-haloethanols (F, Cl and Br) for the Gg′ conformers.     

Far infrared spectra of mono- and bisphthalocyanine derivatives

The far infrared spectra of a series of unsubstituted monophthalocyanine (Pc) and di-Pc derivatives and some of the corresponding tetra-tert-butyl substituted Pc molecules are reported. The infrared data were recorded between 100 and 4.50 cm⁻¹. The vibrational assignment of metal-nitrogen stretching frequencies is discussed. The far infrared data for tert-butyl Pc derivatives and a group of C_4ν Pc complexes are presented here for the first time.     

Far infrared spectra of liquid and solid benzene

The far infrared spectra of liquid and solid benzene are compared. The benzene was maintained at a temperature of 330 K and the applied pressure varied to alter the state. Liquid benzene is observed to possess a structure resembling that of the solid, close to the melting point.     

Far infrared study of some mono- and disaccharides

Some mono- and disaccharides were studied using the far infrared (FIR) spectroscopic method. Results show that every saccharide has a characteristic spectrum pattern. It is useful to distinguish between different saccharides based on the sequence of their relative intensities. Therefore, an encoding method was suggested to label each substance. In this investigation, the FIR spectra of the saccharides were demonstrated using the encoding method and prove the feasibility of the method.     

Far infrared study of polymorphism of trimethylchlorosilane

The far infrared spectra in the range of 16 – 500 cm^?1 for (CH₃)₃SiCl were measured in the temperature range of 90 – 300 K by the use of Fourier transform technique. Two solid phases were found, the high-temperature phase being easily supercooled down to liquid nitrogen temperature. On the basis of the characteristic features of the spectra suggestions concerning the structure of the low-temperature phase are given.     

Far infrared reflection spectra of layered semiconductors

Far infrared reflection and Raman spectra of InSe were measured at 5, 77 and 300 K. Phonon frequencies obtained by reflection spectra were well explained by two-point phonon combination. The crystal structure of-type was confirmed at low temperature. Ion blocking analysis supported also no change of phase by temperature in this semiconductor.     

Far infrared fourier transform spectroscopy of semiconductors

Fourier transform spectroscopy (FTS) is one of the most important tools in the study of shallow level donors and acceptors in semiconductors. When combined with a two-step photothermal ionization process detected photoconductively, FTS allows measurement of optical transitions of donor-bound electrons (and acceptor-bound holes) in ultra-pure germanium samples with impurity concentrations <10⁹ cm^–3 (i.e. one electrically active impurity in 4×10¹³ host atoms). The experimental high resolution study of the hydrogen-like excited state series of shallow levels has yielded as many as 19 lines of width as small as 10eV for some centers. These results have stimulated theoretical work which has led to the unambiguous assignment of quantum states to many bound excited states. Extensive studies of ultra-pure Ge crystals grown under different well-controlled conditions have led to the discovery of a large number of novel shallow impurity complexes. Study of the multiplicities and symmetries of the associated electronic states has led to a detailed understanding of the unusual static and dynamic structures of these novel centers. The chemical composition has been deduced from correlations between the concentration of a particular center and the materials involved in crystal gowth. Isotopic substitution of hydrogen with deuterium has led to the unambiguous proof of the presence of hydrogen in several of the novel centers. In addition to the high resolution spectra of shallow electronic levels, vibrational spectra of bond-centered interstitial oxygen in ultra-pure Ge are noteworthy for their extraordinarily sharp lines.     

Far infrared reflectivity of narrow band materials

The application of a Fourier spectrometer to the study of the electronic structure in the far infrared of some intermediate valence or heavy fermion materials or of highT _c superconductors showed that FT-reflectivity is a powerful tool of investigation at very low energies. A very careful control of the experimental conditions and of the reference measurements is necessary to eliminate spurious reflectivities.The results show optical transitions at very low energy and permit to evaluate the electronic structures and the effective mass of the carriers in the vicinity of the Fermi level.     

Far infrared spectra of solid molecular nitrogen

This paper reports the observation of the far infrared absorption spectrum of a single crystal of N₂, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm^–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed.     

Rotational spectrum and conformational composition of cyanoacetaldehyde, a compound of potential prebiotic and astrochemical interest

The rotational spectrum of cyanoacetaldehyde (NCCH(2)CHO) has been investigated in the 19.5-80.5 and 150-500 GHz spectral regions. It is found that cyanoacetaldehyde is strongly preferred over its tautomer cyanovinylalcohol (NCCH═CHOH) in the gas phase. The spectra of two rotameric forms of cyanoacetaldehyde produced by rotation about the central C-C bond have been assigned. The C-C-C-O dihedral angle has an unusual value of 151(3)° from the synperiplanar (0°) position in one of the conformers denoted I, while this dihedral angle is exactly synperiplanar in the second rotamer called II, which therefore has C(s) symmetry. Conformer I is found to be preferred over II by 2.9(8) kJ/mol from relative intensity measurements. A double minimum potential for rotation about the central C-C bond with a small barrier maximum at the exact antiperiplanar (180°) position leads to Coriolis perturbations in the rotational spectrum of conformer I. Selected transitions of I were fitted to a Hamiltonian allowing for this sort of interaction, and the separation between the two lowest vibrational states was determined to be 58794(14) MHz [1.96112(5) cm(-1)]. Attempts to include additional transitions in the fits using this Hamiltonian failed, and it is concluded that it lacks interaction terms to account satisfactorily for all the observed transitions. The situation was different for II. More than 2000 transitions were assigned and fitted to the usual Watson Hamiltonian, which allowed very accurate values to be determined not only for the rotational constants, but for many centrifugal distortion constants as well. Two vibrationally excited states were also assigned for this form. Theoretical calculations were performed at the B3LYP, MP2, and CCSD levels of theory using large basis sets to augment the experimental work. The predictions of these calculations turned out to be in good agreement with most experimental results.