Raman spectra of proton ordered phase XI of ICE I. Translational vibrations below 350 cm(-1)

Polarized Raman spectra from single crystals of ice XI (proton ordered phase of ice Ih) were measured and assigned for the modes below 350 cm(-1) in the translational vibration region. In contrast to the proton disordered ice Ih, the spectra in ice XI show clear polarization dependence and several new peaks are observed. Most of the vibrational modes were successfully assigned by the simplified point mass model with the symmetry C(2v) (12)(Cmc2(1)) and by the depolarization effect. In particular, LO-TO splitting of the mode near 240 cm(-1) was experimentally confirmed for the first time, which indicates that the long range force effect appears distinctly in ice XI.     

Vibrational spectra of 1:2 ordered perovskites

The infrared and Raman spectra of some perovskites with general formula A₃BB′₂O₉ are reported, viz. Sr₃MgNb₂O₉, Sr₃CaNb₂O₉, Pb₃MgNb₂O₉, and Ba₃Gd₂WO₉. The interpretation is by far not as simple as for 1:1 ordered perovskites. Only a rough assignment of the internal modes of the niobate and tungstate octahedra can be made. The spectra of the niobates are very sensitive to the degree of order between the divalent metal ions and the Nb⁵⁺ ions among the smaller cation sublattice. This is evaluated qualitatively.     

Vibrational overtone spectroscopy of jet-cooled methanol from 5000 to 14 000 cm(-1)

Spectra of jet-cooled methanol in the overtone and combination region from 5000 to 14 000 cm(-1) have been obtained by means of infrared laser-assisted photofragment spectroscopy. Many of the observed features are assigned to combination bands of the type nnu(1)+nu(6), nnu(1)+nu(8), and nnu(1)+nu(6)+nu(8) (n=1,2,3), where nu(1) is the OH stretch, nu(6) is the OH bend, and nu(8) is the CO stretch. These bands show sharp torsion-rotation structure with features as narrow as 0.1 cm(-1). We also observe CH stretch overtones that are weaker than the OH containing combination bands and lack distinct torsion-rotation structure above v(CH)=2. The extent of observed structure on these bands allows us to place limits on the intramolecular vibrational energy redistribution decay rates in the upper vibrational states. We report a global fit of the observed band centers to a simple expression involving low-order anharmonicity constants.     

Gas phase spectroscopy of HNO3 in the region 2000-8500 cm(-1)

Spectra of gas phase HNO3 were collected in the region 2000-8500 cm(-1) using Fourier-transform infrared spectroscopy. This region is dominated by the nu1 O-H stretching mode but also contains many previously unreported combination bands and overtones. This work marks the first observation of Fermi resonance the 2nu1 O-H stretching overtone. Previously unobserved bands were assigned and integrated intensities were obtained. For bands already reported in the literature, comparisons of relative intensities are presented when possible. This work gives a brief discussion on the trends in overtone intensities and on mode mixing in HNO3 in relation to previous experimental and theoretical studies.     

Vibrational analysis of the Raman,infrared and electronic spectra of hexafluoromanganate(IV)

From the Raman, infrared and electronic spectra all of the fundamental vibrational frequencies were determined for both the ground state⁴ A _2g and the excited² E _g In addition some fundamental frequencies were established for the⁴ T _2g and⁴ T _1g excited states from low temperature absorption spectra.

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Zusammenfassung Aus den Raman-, Infrarot- und Elektronenspektren wurden alle Grundschwingungsfrequenzen für den Grundzustand⁴ A _2g und den angeregten² E _g-Zustand bestimmt. Ferner wurden noch einige der entsprechenden Größen für die angeregten Zustände⁴ T _2g und⁴ T _1g aus Tieftemperatur-Absorptionsspektren ermittelt.

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Résumé Toutes les fréquences fondamentales de vibration ont été déterminées pour l'état fondamental⁴ A _2g et l'état excité² E _g à partir des spectres Raman, infra-rouge et électronique. De plus, certaines fréquences fondamentales des états excités⁴ T _2g et⁴ T _1g ont été obtenues à partir des spectres d'absorption à basse température.

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Dedicated to the memory of Prof. Hans-Ludwig Schläfer.     

Complete experimental rovibrational eigenenergies of HCN up to 6880 cm(-1) above the ground state

The [H,C,N] molecular system is a very important model system to many fields of chemical physics and the experimental characterization of highly excited vibrational states of this molecular system is of special interest. This paper reports the experimental characterization of all 3822 eigenenergies up to 6880 cm(-1) relative to the ground state in the HCN part of the potential surface using high temperature hot gas emission spectroscopy. The spectroscopic constants for the first 71 vibrational states including highly excited bending vibrations up to v(2) = 10 are reported. The perturbed eigenenergies for all 20 rotational perturbations in the reported eigenenergy range have been determined. The 11,070 eigenenergies up to J = 90 for the first 123 vibrational substates are included as supplement to this paper. We show that a complete ab initio rovibrational analysis for a polyatomic molecule is possible. Using such an analysis we can understand the molecular physics behind the Schro?dinger equation for problems for which perturbation theoretical calculations are no more valid. We show that the vibrational structure of the linear HCN molecule persists approximately up to the isomerization barrier and only above the barrier the accommodation of the vibrational states to the double well structure of the potential takes place.     

Complete experimental rovibrational eigenenergies of HNC up to 3743 cm(-1) above the ground state

The [H,C,N] system is one of the ideal candidate molecules to test new models aimed to calculate the manifold of the rotational, vibrational, and electronic states of a triatomic molecule. The isomerization reaction HCN?HNC is one of the most important model systems for the study of unimolecular reactions. This paper reports on the experimental characterization of all 1191 eigenenergies up to 3743 cm(-1) relative to the ground state in the HNC part of the potential surface using high temperature hot gas emission spectroscopy. The spectroscopic constants for the first 27 vibrational states including highly excited bending vibrations up to v(2) = 7 are reported. The first 14 rotational perturbations have been identified and the perturbed eigenenergies were determined. The 3200 eigenenergies up to J = 70 for the first 47 vibrational substates are included as supplement to this paper.     

Vibrational assignment of the normal modes of 2-phenyl-4-(4-methoxy benzylidene)-2-oxazolin-5-one via FTIR and Raman spectra, and ab inito calculations

Raman and FTIR spectra of 2-phenyl-4-(4-methoxy benzylidene)-2-oxazolin-5-one were recorded in the regions, 100-3300 and 400-4000 cm(-1), respectively. Vibrational frequencies and intensities of the fundamental modes of this hetrocyclic organic molecule were computed using ab initio as well as AM1 semiempirical molecular orbital methods. Ab initio calculations were carried out with basis set up to RHF/6-311G. Conformational studies regarding the effect of moving the methoxy group in the 2-phenyl-4-(4-methoxy benzylidene)-2-oxazolin-5-one molecule to a different position on the ring was also carried out. Observed vibrational wavenumbers were found to be mostly consistent with ab initio values. The most intense mode of vibration observed at 1250 cm(-1) in Raman spectra, also observed as a strong band in FTIR, was assigned as C-O stretching vibration in the methoxy group. Asymmetric stretching vibrations between CC and CN bonds was predicted as most intense mode by our ab initio calculation.     

Vibrational (i.r. and Raman) spectra and conformational studies of 1-formyl-3-thiosemicarbazide

The i.r. and Raman spectra (30–4000 cm⁻¹) of 1-formyl-3-thiosemicarbazide (FTSC) and deuterated ftsc-d₄, have been studied. Most of the vibration modes reveal pairs of bands and show strong temperature dependence. A band group {ν(NNH₂)} at ∼ 1100 cm⁻¹ exhibits well resolved doublet (1095 and 1112 cm⁻¹) structure below 100 k. The intensity in the 11 12 cm⁻¹ band decreases regularly (band disappears at 150 K) with the rise in temperature. Two new bands at 955 and 1070 cm⁻¹ appear while measured above 400 K. The system eventually exists in several conformers in simultaneous equilibria. Moreover, a few bands {e.g. ν(CO), ν(CS) and ν(CH)} that show strong intensifies in i.r. exhibit weak (or zero) intensifies in the Raman and vice-versa. The features (characteristic of u and g vibration species) could be explained by a C_2h pseudo symmetry space group proposed for the system. Both the FTSC and FTSC-d₄ represent strong molecular associations. This favours the maximum abundance in the dimer stabilized conformers.     

Raman spectra of gas hydrates--differences and analogies to ice 1h and (gas saturated) water

It is generally accepted that Raman spectroscopic investigations of gas hydrates provide vital information regarding the structure of the hydrate, hydrate composition and cage occupancies, but most research is focused on the vibrational spectra of the guest molecules. We show that the shape and position of the Raman signals of the host molecules (H(2)O) also contain useful additional information. In this study, Raman spectra (200-4000 cm(-1)) of (mixed) gas hydrates with variable compositions and different structures are presented. The bands in the OH stretching region (3000-3800 cm(-1)), the O-H bending region (1600-1700 cm(-1)) and the O-O hydrogen bonded stretching region (100-400 cm(-1)) are compared with the corresponding bands in Raman spectra of ice Ih and liquid water. The interpretation of the differences and similarities with respect to the crystal structure and possible interactions between guest and host molecules are presented.     

Raman spectra of high pressure phase and phase transition of polytetrafluoroethylene (teflon)

Raman spectra of phases II and III of crystalline polytetrafluoroethylene at room temperature and several pressures to 35 kbar are reported and discussed in terms of the information provided about molecular conformation, crystal structures, and the phase transition. A revised vibrational assignment is reported for phase II spectra which suggests that the 1215- and 1295-cm^?1 bands are not fundamentals but are combinations of overtones with A₁ symmetry of a cyclic group.     

On the interpretation of the 1100 cm(-1) Raman band in phospholipids and other alkyl-containing molecular entities

The long-standing issue on the interpretation of a Raman band at 1100 cm(-1) is discussed. By combining observations from studies on lipid bilayers, alkanes, and polyethylenes, one can now definitely assign this band to the presence of isolated gauche bonds. In addition, we discuss the use of an order parameter S(trans) in lipid bilayer structures.     

Optical spectroscopy of RuC: 18,000-24,000 cm(-1)

The optical spectrum of diatomic RuC has been recorded from 17 800 to 24 200 cm(-1). Three previously unidentified excited electronic states were analyzed and identified as having Omega' = 0, Omega' = 2, and Omega' = 3. The Omega' = 3 state was determined to be a 3Delta3 state that is suggested to arise from a mixture of the 10sigma(2)11sigma(2)5pi(3)2delta(3)12sigma(1)6pi(1) and 10sigma(2)11sigma(1)5pi(3)2delta(3)12sigma(2)6pi(1) electronic configurations. Three additional bands belonging to the previously observed [18.1] (1)Pi<--X (1)Sigma(+) system were analyzed to obtain B(e) (')=0.558 244(48) cm(-1), alpha(e) (')=0.004 655(27) cm(-1), omegae' = 887.201(37) cm(-1), and omega(e) 'xe' = 5.589(7) cm(-1) for the 102Ru 12C isotopomer (1sigma error limits). A Rydberg-Klein-Rees analysis was then performed using the determined spectroscopic constants of the [18.1] 1Pi state, and similar analyses were performed for the previously observed states. The resulting potential energy curves are provided for the 100Ru 12C, 101Ru 12C, 102Ru 12C, and 104Ru 12C isotopic species.     

The Raman spectra of the KOH-doped ice polymorphs: V and VI

The effect on the Raman spectra of the proton ordering induced by KOH in the high pressure phases of ice, ice V and VI has been studied. Our previous Raman studies of ice V and ice VI (ref.1) showed spectroscopic evidence of partial proton ordering at low temperatures (below about 130 K) in ice V and a possible phase change in ice VI. These conclusions were made on the measurements of the lattice vibration region. The present results, based on the observation of the bands due to the uncoupled O-D stretching vibrations of KOH-doped ice V and, in particular, ice VI, show that some kind of proton ordering or partial proton ordering may be induced by the presence of KOH dopant in these two ices.A Lorentzian curve fit has been used to separate the main band from the side bands in the relatively complex structured band due to the uncoupled O-D stretching vibration in ice V and ice VI.     

Vibrational coherence from the dipyridine complex of bacteriochlorophyll a: intramolecular modes in the 10-220-cm(-1) regime, intermolecular solvent modes, and relevance to photosynthesis

We present the first observations of vibrational coherence in the 10-220-cm-1 region from bacteriochlorophyll a (BChl) in solution. A distinction can be made for the first time between BChl's intramolecular normal modes and intermolecular modes between BChl and solvent. The results show that the low-frequency vibrations that accompany the initial electron-transfer reaction from the paired BChl primary electron donor, P, in photosynthetic reaction centers arise predominantly from intramolecular modes of histidine-ligated BChl macrocycles. The results also suggest that polar-solvent interactions can significantly perturb the electronic properties of BChl in a manner that might have important functional consequences.     

The structure of liquid water. A low frequency (10–400 cm) Raman study

The recently developed molecular form of the ground state inversion potential method (GIPM) is applied here to the calculation of the total subshell photoionization cross sections of the water molecule in the energy range from threshold to 50 eV. The results show that the ionization can be accurately represented as a superposition of atomic processes.     

Vibrational spectra of tris(dmit) complexes of main group metals: infrared, Raman and ab initio calculations

Infrared Fourier Transform investigation of several metal tris-complexes of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) ligand have been recorded within a theoretical-experimental investigation of the vibrational molecular spectra of crystalline [NEt4]2[Sn(dmit)3] and [NEt4][Sb(dmit)3] compounds. For the [Sn(dmit)3]-2 anion we recorded as well the Raman Fourier Transform spectra. Ab initio calculations have been carried with several ECPs, basis sets and methodologies (RHF and DFT) in order to assess family and methodological errors precisely. Geometry optimization and subsequent hessian calculation lead to the vibration frequencies reported. These calculated frequencies and intensities assisted the fundamental, overtones and combinations bands assignments. Remarkable agreement has been found between the experimental geometries and frequencies to those here calculated. Besides the bands traditionally studied for the dmit compounds, as CC and CS stretchings, also the region below 500 cm(-1) was evaluated, allowing to characterize several modes involving angular deformation of the dmit as the MS stretching of these octahedral distorted systems.     

Vibrational spectra and normal coordinate analysis of Ni and Zn complexes with 1-(2-pyridylazo)-2-naphthol

Infrared and resonance Raman spectra of Ni(PAN)₂ and Zn(PAN)₂ (where PAN denotes 1-(2-pyridylazo)-2-naphthol) have been measured in the solid state. In addition, the nickel complex dissolved in CS₂ has also been investigated by Raman spectroscopy at room temperature and 16 K. A normal coordinate analysis was performed to characterize the observed vibrational transitions in terms of potential energy distribution.     

Vibrational spectra of 2 (3H) benzofuranone studied by Raman,IR spectroscopy and AM1 semiempirical molecular orbital calculations

Raman spectra of 2 (3H) benzofuranone have been recorded in the region 400-3200 cm(-1) and the IR spectra have been recorded in the region 200-4000 cm(-1). Vibrational frequencies for the fundamental modes of this bicyclic heteroatomic molecule have also been calculated using Austin method 1 (AM1) semiempirical molecular orbital method. Vibrational assignments have been made for the fundamental modes and the observed combination and overtone bands are also assigned. A splitting in the carbonyl group (C=O stretching) frequency observed at 1640-1660 cm(-1) in both Raman and IR spectra, is explained as Fermi-resonance. Net atomic charges for each atom of this molecule along with its heat of formation were also calculated. It is evident from the calculations that the 2 (3H) benzofuranone is more stable than the 3 (2H) benzofuranone in contrast to earlier estimates.