Theoretical prediction of vibrational spectra: The out-of-plane force field and vibrational spectra of pyridine

The harmonic force field for the out-of-plane vibrations of pyridine has been calculated from ab initio Hartree-Fock wavefunctions obtained with a 4–21 basis set of contracted Gaussians. To account for systematic errors, the calculated force constants were scaled, using only two independent sclae factors which were transferred unchanged from benzene. The resulting scaled quantum mechanical force field, which is strictly a priori in that it is not based on any experimental data on pyridine, predicts the 64 out-of-plane fundamental frequencies of pyridine and its deuterated isotopomers of C_2v symmetry with a mean deviation from experiment of only 8.5 cm^?1. Addition of polarization functions to the basis set for the nitrogen atom and refinement of the two scale factors by fitting them to the observed pyridine spectra produce no significant improvement in the fit. Assignments of the vibrational spectra are discussed.     

The computed force constants and vibrational spectra of cubane

The geometry, complete harmonic force field, and dipole moment derivatives of cubane, C₈H₈, have been calculated at the Hartree-Fock level using a 4–21 Gaussian basis set. The infrared and Raman spectra of cubane and four deuterated derivatives were calculated and compared with previously observed spectra. A set of five scale factors for the calculated force constants was then derived by least-squares fitting of the fundamental vibrational frequencies calculated from the scaled force field to the frequencies obtained by direct experimental measurement. The resulting scaled quantum-mechanical (SQM) force field, containing 73 unique elements, is believed to give an accurate representation of the harmonic vibrational potential of cubane. In most cases, the spectral assignments previously made from purely empirical considerations were confirmed, but a few corrections are proposed. The only major alteration is for an A_2u mode revised to appear at 1030 cm^?1 in the undeuterated molecule. Coriolis constants and approximate infrared intensities are also calculated.     

Infrared spectra of matrix isolated BH3NH3, BD3ND3, and BH3ND3

The infrared spectra of ammonia-borane, BH₃NH₃, and two of its deuterated isotropic species, BD₃ND₃ and BH₃ND₃, isolated in argon matrix at liquid hydrogen temperature have been measured. Well resolved bands for these three isotopic species have been observed for all the fundamentals. A complete frequency assignment based on C₃v molecular symmetry has been made. A set of force constants have been calculated from the data for the two isotopes BH₃NH₃ and BD₃ND₃ using a valence force field. The agreement between experiment and frequencies calculated from these force constants for the mixed isotopic species, BH₃ND₃, substantiates the present assignment.     

Formate anion: The physical force field

Unequivocal assignments for all of the vibrational modes of the formate ion have been made from isotopic shifts measured in the Fourier transform infrared and Raman spectra of polycrystalline samples of the sodium salts of HCO₂^?, H¹³CO₂^?, DCO₂^?, and D¹³CO₂^?. Literature frequencies for DCO¹⁸O^? and DC¹⁸O₂^? have been added to the above results for the unique determination of the 10 force constants in the general harmonic force field. Product rule relations among the harmonic frequencies are shown to interfere seriously with the determination of the physical force field by the standard normal coordinate computation. The least-squares refinement is found to be particularly sensitive to identified types of anharmonic error in the frequencies. Refinements characterized as Φ^aH and Φ^aD improve reliability by elimination of the deuterium isotopic shift for νCH. The physical force field is interpreted in terms of the geometric and electronic structure.     

Methanol and deuterated species: Infrared data,valence force field,rotamers, and conformation

New infrared measurements of gaseous and matrix-isolated methanol and 7 deuterated species are presented and analyzed. A revised assignment for the species CH₃OH(D) and CD₃OH(D) is used to determine 15 significant parameters of a valence force field by a converged simultaneous least-squares adjustment to 44 observed fundamentals. The respective frequencies calculated for the rotamers of CH₂DOH(D) and CHD₂OH(D) turn out to be a valid prediction as they are used to assign 78 observed fundamentals of the species with partially deuterated methyl groups. The values of the 15 force constant parameters are refined by including all 122 observed fundamentals. The force field contains significant deviations from local C_3v symmetry of the methyl group. Such an asymmetry, in the CH-stretching diagonal part, produces a difference of about 10 cm^?1 in the zero point energy of symmetric and asymmetric rotamers of the species with partially deuterated methyl groups. Calculations based on equilibrium structures with and without methyl tilt yield better agreement with observed data in the nontilted case. A preliminary calculation of relative intensities reproduces the major effects of isotopic substitution and rotational isomerism. Experimental evidence for the staggered conformation is obtained from a comparison of observed data with calculated results based on staggered and eclipsed models.     

Absorptionsspektren von Er3+ in InCl3 und in ScCl3

The optical absorption spectra of Er³⁺ in single crystals of InCl₃ and ScCl₃ have been obtained between 14,000 and 29,000 cm^?1. The observed crystal field splittings are interpreted in terms of crystal potential of symmetry 3m for ScCl₃ and of symmetry 2m for InCl₃. There is however found, that for both cases the splittings will be approximately explained by a crystal potential of cubic symmetry. The employed hostlattices are of special interest, because the ions of the iron series can occupy the same sites as the rare earth ions.     

Raman,Infrared and 1H-NMR Spectra of Hexamethyldisilylchalcogenides

The Raman, infrared and ¹H-NMR spectra of (CH₃)₃ -X-Si (CH₃)₃ (X=O,S,Se,Te) were measured, and the assignment was carried out by comparison with those of the structurally related compounds, (CH₃)₃ SiCl and (CH₃)₃ Si-Si (CH₃)₃. The vibrational spectra of (CH₃)₃ Si-X-Si (CH₃)₃ can be interpreted in terms of a non-rigid D_3d symmetry with internal rotations, because those of skeletones of the molecules indicate the lack of coincidence between Raman and infrared frequencies. The ¹H-NMR spectra also support a non-rigid D_3d model, because only one band for CH₃ group appears.     

Harmonic Frequencies and Potential Energy Distributions of Partially Deuterated Methyl Cyanide

Although the vibrational spectra and force constants of CH₃CN and CD₃CN have been thoroughly studied, partially deuterated methyl cyanide has received much less attention. The infrared spectrum of CD₂HCN has only recently been reported1 and that of CH2DCN has not yet appeared. Normal coordinate analysis for neither partially deuterated species has appeared. We report here harmonic frequencies and potential energy distributions for both partially deuterated methyl cyanide species, CH₂DCN and CD₂HCN, based on force fields and structural parameters from CH₃CN and CD₃CN. The calculated frequencies for CD₂HCN are compared with the observed infrared frequencies. The vibrational interaction of the relatively high CN stretching frequency and the CD stretching frequencies is also discussed.     

Application of self-consistent-field ab initio calculations to organic molecules

The local symmetry force constants of propene have been calculated from extended (4–31 G) self-consistent-field ab initio energies. The previously developed scaling method was used to adjust seven scale factors on 84 observed frequencies of propene and deuterated analogues. The latter were taken from the literature. The average difference between observed and calculated frequencies amounted to 8·3 cm^-1 or 0·63 per cent. The stretching force constant of the carbon-carbon single bond was found to be 0·3–0·4 mdyn Å^-1 larger than those of ethane and propane. Force constants of the CH₃ groups in the series: ethane, propane, propene, methanol and dimethyl ether, written in local symmetry coordinates, seem to be transferable within about 2 per cent. Individual CH bond stretching force constants, written in internal coordinates, show significant chemical variations.     

Study of the P-T phase diagram of pyridinium perchlorate by X-ray diffraction and Raman spectroscopy

The crystal structure and vibrational spectra of deuterated pyridinium perchlorate (d ₅PyH)ClO₄ (C₅D₅NHClO₄) are studied by means of neutron diffraction in ambient conditions, X-ray diffraction at high pressures up to 3.5 GPa in the temperature range 297–420 K, and Raman spectroscopy at high pressures up to 5.7 GPa. Deuterated pyridinium perchlorate at ambient conditions has rhombohedral structure with the R3m symmetry (paraelectric phase I). Over the pressure range of 0.5–1.2 GPa, the phase II with monoclinic symmetry Cm exists. At pressure P ～ 1.2 GPa, the phase transition to monoclinic phase III with the Pm symmetry is observed at ambient temperature. The lattice parameters, unit cell volume, and frequencies of internal vibrational modes as functions of pressure are obtained for different phases of deuterated pyridinium perchlorate. The P-T phase diagram of (d ₅PyH)ClO₄ over the extended pressure and temperature range is discussed.     

Microwave spectra of deuterated arsines: Distortion moment transitions of AsD3, microwave spectra of AsH2D and AsHD2, and the structure of arsine

Microwave spectra of three deuterated arsines have been measured and analysed. For AsD₃ distortion moment transitions have been observed for the first time, in the form of the K = ±1 ← ∓2 cluster; their frequencies have been combined with those of previously observed “normal” transitions to give rotational, centrifugal distortion, and ⁷⁵As hyperfine constants. For AsH₂D and AsHD₂, the measurements have been extended considerably and now include for the first time R-branch transitions; similar spectroscopic constants have been evaluated. The data have been combined with earlier results for AsH₃ and with vibrational data in a harmonic force field analysis. Both ground state average (r_z) and equilbbrium (r_e) structures have been estimated.     

Vibrational Behaviour of the CrO3- 4 Anion in Different Crystalline Environments

The powder-infrared spectra of different crystalline compounds containing the tetrahedral Cro^3- ₄, anion have been recorded and analyzed with the aid of the site symmetry rules. In some cases Raman data are also reported. The effect of the different crystalline environments is discussed in detail and comparisons with isostructural phases are also made. A definitive assignment for the internal vibrations of the CrO^3- ₄, ion is proposed and a new set of force constants has been calculated fron a modified valence force field.     

Reinvestigation of Microwave Spectrum of Ethylsilane: II. Vibrationally Excited States and Internal Rotations

Microwave spectra of ethylsilane and its three deuterated species in vibrationally excited states have been measured. A least-squares analysis of the observed frequencies gave rotational constants and three of the quartic centrifugal distortion constants. The barriers to the internal rotation of both the methyl and silyl groups and the coefficients of the potential cross terms were solved from splittings of the multiplets.The averages of CH₃ and SiH₃ barriers were determined to be 2634±16 and 1992±21 cal/mol and the potential cross terms, V₁₂ and V′₁₂, were estimated to be −55 and −111 cal/mol, respectively, for the four species.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

Fluorescence and fluorescence excitation spectra of jet-cooled carbazole

The fluorescence excitation spectra of jet-cooled carbazole molecules at vibrational temperatures of 55 and 80 K and the fluorescence spectrum of these molecules excited by radiation at the frequency of a pure electronic transition are measured. As the vibrational temperature increases, the excitation spectra exhibit a series of lines of the same symmetry, which are caused by the interaction of the active vibration with a subensemble of optically inactive vibrations. The final symmetry of the totally and nontotally symmetric vibrations is determined from the shape of the rotational contours of the lines of vibronic transitions. The values of a decrease in the frequency of the nontotally symmetric vibrations in the first excited electronic state S ₁ due to their interaction with the electronic state S ₂ are calculated to be up to 100 cm^?1. The frequencies of the pure electronic transitions in the absorption and fluorescence spectra coincide with each other and are equal to 30809 cm^?1, the frequencies of vibrations in the ground state S ₀ exceeding the frequencies of the corresponding vibrations in the excited state S ₁. The degree of polarization of the integral fluorescence is determined for a series of vibronic transitions of the a ₁ and b ₂ final symmetry that are observed in the fluorescence excitation spectra, and the contribution of the intensity with the borrowed polarization θ_⊥ to the integral fluorescence is calculated. It is found that the intensity θ_⊥ is higher for the transitions of the b ₂ symmetry and can reach ≈50%.     

Molecular vibrations and lattice dynamics of ortho-terphenyl

Infrared and Raman spectra of crystalline, melted and solvated ortho-terphenyl and its perdeuterated isotopomer, D₁₄-ortho-tephenyl, have been recorded. Optimized geometries and vibrational frequencies were calculated by the semiempirical RHF/AM1 method and by DFT using the B3LYP functional and 6–31G(d) basis set. In both cases the lowest energy conformation is of C₂ symmetry. With the scaled AM1 and B3LYP/6-31G(d) force fields the average error in reproducing the experimental molecular vibrational frequencies is 13cm^?1 and 5cm^?1, respectively. The AM1 potential energy surface for phenyl torsions was mapped on a 15° grid. The barrier to concerted internal rotation is estimated to lie between 3 kJ mol^?1 and 6kJ mol^?1. The calculations of the lattice dynamics at k = 0 in the low temperature fully ordered crystal phase of parent and deuterated ortho-terphenyl were performed with inclusion of six low lying intramolecular vibrations. The conformational change of the ortho-terphenyl molecule induced by crystal packing forces was taken into account by re-defining the unperturbed molecular vibrational state. Although an accurate assignment of lattice vibrations was not possible, the calculated spectra give quite a reasonable picture of the low frequency dynamics in crystalline ortho-terphenyl. The relevance of the results obtained to the glass forming property of ortho-terphenyl is discussed.     

Light-induced isomerization and photochemical transformation of methylformate in an argon matrix. Vibrational frequencies,force field,and normal coordinate analysis of trans-methylformate

When methylformate (HCOOCH₃), isolated in an argon matrix, is excited into the $\text{S}{}_1\text{(ππ}{}^1\text{) ← S}{}_0$ transition at 248 nm the prevailing cis conformer is transformed into the trans conformer. In a consecutive photolysis step the latter is decomposed to stable products including a hydrogen-bonded (1:1) complex between CO and methanol, acetic acid, and CO₂ and methane. The efficient photolytic preparation of the unstable trans-methylformate and its deuterated analogs DCOOCH₃, HCOOCD₃, and DCOOCD₃ in an argon matrix allowed measurement of their ir spectra (170–4000 cm^?1) in great detail thus providing an almost complete set of fundamentals together with a number of combination and overtone frequencies. With a normal coordinate analysis based on a constrained valence force field (transferable valence force field approach) the frequencies of trans-methylformate were assigned and compared to those of the remeasured cis rotamer.     

Studies of coupled molybdate and tungstate vibrations

The polarized Raman and infrared reflection spectra of molybdate and tungstate compounds of barium and strontium are presented and analyzed. The longitudinal and transverse frequencies of the infrared active phonons were calculated by a Kramers-Kronig analysis of the reflection curves. A strain induced forbidden mode was observed in the reflection spectra that gives interpretation of the strong shoulder on the ν₃ bands in the absorption spectra of mulled samples. The correlation field splittings of the internal modes were analyzed in terms of dipole-dipole interaction theory. The correlation field splittings of the ν₃ modes were found to be explainable in terms of dipolar coupling alone, while the splittings of the ν₂ and ν₄ modes could not be accounted for in terms of dipolar coupling.     

Coupling of the CDW and the water mode in K2Pt(CN)4Br0.3⋯3.2H2O

In previous work we have observed the amplitude mode of the charge density wave (CDW) in K₂Pt(CN)₄Br_0.3?3.2H₂O (KCP) by means of Raman scattering. New measurements made on deuterated material, K₂Pt(CN)₄Br_0.3?3.2D₂O (KCP1), show the same mode but shifted from 44 to 38 cm_?1, maintaining the symmetry properties and temperature dependence of frequency and linewidth. This considerable isotope effect is interpreted in terms of a coupling of the CDW with the water stretching mode, which by the deuteration is shifted from 3494 cm^?1 in KCP to 2560 cm^?1 in KCP1 according to the change in atomic mass. Both of these modes exhibit A₁(z) symmetry. At 5 K the resulting decoupled frequency of the CDW amplitude mode is 57 cm^?1, and the coupling energy about 140 cm^?1. A discussion of the temperature dependence of various important quantities is given. The present results show that the water molecules, which are located in between the Pt chains are strongly involved in the eigenvector of the CDW amplitude mode.