Multiple vibrational excitations of H2O and D2O on Si(100)(2 × 1): A HREELS study

The HREELS (high-resolution electron energy-loss spectroscopy) spectra from H₂O and D₂O chemisorbed on the clean Si(100)(2 × 1) surface have been investigated in the energy region between about 500 and 1400 meV. For the first time, second overtones have been observed for a chemisorbed species. This observation is believed to be due to the enhancement of the O-H stretching fundamental and overtone modes because of the temporary formation of a negative ion that occurs when the incident electron is briefly trapped in a shape resonance. Additional multiple and combination modes are observed involving the resonance enhanced overtones as well as the fundamental modes. Furthermore, the dissociation energy of the hydroxyl group has been determined and found to be much larger than the actual energy needed to dissociate hydroxyl groups on the surface, indicating that the driving force for the observed atomic rearrangements is probably Si-O bond formation rather than O-H dissociation.     

IR and Raman studies of cholesterol monohydrate grown in gel medium

IR and Raman spectra of cholesterol monohydrate (C₂₇H₄₆O.H₂O) crystals grown in silica gel have been recorded and analysed. Multiple bands in the O-H frequency stretching region is observed, confirming that the crystal as monohydrate. The crystal is also found to exhibit tautomeric behaviour.     

Fourier Transform Vibrational Spectra of Magnesium Hydrogenphosphate Trihydrate. I. The O-H Stretching Region∗

Abstract

The Fourier transform (FT) infrared and Raman spectra of newberyite, MgHPH₄ - 3H₂O are studied in the region where the stretching vibrations of the water molecules (protiated and deuterated) and the O-H/O-D stretches of the hydrogenphosphate anions are expected to appear. The O-H stretching vibrations give rise to a complex feature known as the A,B,C trio. Since neither of the maxima found below 3000 cm^?1 represents a true band arising from a given fundamental, it is pointless to correlate their frequencies with the observed O…O distances. In the water stretching region, the two bands with highest frequencies undoubtedly correspond to the anti symmetric and symmetric stretch of one type of the water molecules. The stretching vibrations of one of the remaining two types of H₂O molecules are clearly uncoupled and the O-H oscillator involved in the weaker hydrogen bond is responsible for a band at 3376 cm^?1 whereas the rest of the water stretchings are apparently overlapped yielding the complex band below 3320 cm^?1. Thus the situation is again complicated and the correlations between the frequencies and the O_w…O distances are inappropriate. The two bands at highest frequencies (3522 and 3483 cm^?1 at RT) exhibit a positive temperature coefficient.

     

Temperature dependent water adsorption on Bi2Sr2CaCu2O8 single crystal

Temperature dependent infrared study of water adsorption on the bc-plane of a Bi₂Sr₂CaCu₂O₈ (Bi2212) single crystal reveals that water is molecularly physisorbed, and forms hydrogen-bonded clusters in the temperature range of 85-150 K. Although dissociative adsorption is expected on surfaces terminated with Ca-O and Cu-O groups, no dissociated species is detected. The main absorption bands occur between 3200 and 3500 cm⁻¹ and are assigned to the O-H stretching and the overtone of O-H bending. For exposures higher than 1.0 L, the sticking coefficients are similar for different temperatures. The features in the O-H stretch region for water clusters red-shift as a function of temperature between 85 and 140 K. Water clusters have an amorphous structure between 85 and 140 K, and form a crystalline structure at 150 K.     

Vibrational study of H3OUO2PO4·3 H2O (HUP) and related compounds. Phase transitions and conductivity mechanism: Part II,H3OUO2PO4·3 H2O

Infrared and Raman spectra of polycrystalline H₃OUO₂PO₄·3 H₂O (HUP) and its D and P¹⁸O₄ derivatives, in the form of dense transparent disks and wet powder, have been investigated at various temperatures in the 100–300 K region. The bands due to framework vibrations are similar to those of KUP, whereas those for the protonic species are different. OH stretching and bending bands of the oxonium ion have been identified at 2920, 1740 and 1160 cm^?1 in the low-temperature spectrum of HUP. Differential scanning calorimetry (DSC) and infrared (IR) intensity investigations show a phase transition between 274 and 260 K. The mechanism of the phase transition consists, as in the case of KUP, of ordering of the protonic species, which induces ordering of PO₄ tetrahedra. The ordering can be influenced by excess water content, stacking faults and stress (ferroelastic behaviour is evidenced). The conductivity mechanism in HUP is discussed.     

High-Resolution IR Spectroscopy of the N2O-H2O and N2O-D2O van der Waals Complexes

We report high-resolution infrared vibrational-rotational spectra of the weakly bound complexes N₂O-H₂O and N₂O-D₂O in the higher frequency N₂O stretching mode region (ν₃=2223.756693(124) cm⁻¹). The measurements were carried out using a free jet expansion in combination with a lead salt diode laser spectrometer. Rotational constants, quartic centrifugal distortion constants, and band origins have been derived for both isotopomers. The geometrical structure is determined using isotopic substitution. The deduced structure shows evidence for a second hydrogen bond interaction within the complex. The nonrigidity of the complexes gives rise to an internal rotation of the water molecule around its own C_2v symmetry axis. For N₂O-H₂O, a tunneling splitting arising from this internal motion has been observed in the spectra. According to symmetry considerations, the observed splitting in the spectrum of N₂O-H₂O corresponds to the difference between the tunneling frequencies in the ground and vibrationally excited states.     

A new type of phase transition in M(ClO4)2(H2O)6M = Fe,Co, Ni and Mn

Mössbauer studies on Fe(ClO₄)₂(H₂O)₆ salt showed anomalous quadrupole splitting around (230 ± 15)°K which we have established to be due to a new type of phase transition from pseudohexagonal to monoclinic system. Exactly similar type of transition was observed magnetically in all the isomorphous Ni²⁺, Co²⁺ and Mn²⁺ perchlorate hexahydrate single crystals at different critical temperatures.     

The IR and Raman spectra of Tb0.2Dy0.9Gd0.9(MoO4)3

The IR and Raman spectra of the ternary molybdate Tb_0.2Dy_0.9Gd_0.9(MoO₄)₃ have been recorded and analysed on the basis of the vibrations of MoO²⁻₄ ions. The splitting of the non-degenerate Mo—O symmetric stretching mode due to the vibrational interaction between neighbouring ions is observed. The large splitting observed for the v₃(F₂) mode is probably due to the large number of MoO²⁻₄ ions and strong interlayer coupling present in the unit cell.     

The Raman spectra and cross-sections of H2O, D2O, and HDO in the OH/OD stretching regions

We report the OH and OD stretching regions of the vapor phase Raman spectra of H₂O, and of a D₂O/HDO mixture, at room temperature. Also, the corresponding spectrum of H₂O at ∼2000 K in a methane/air flame is reported. These spectra are interpreted in terms of transition moments of the molecular polarizability, based on high-level ab initio calculations of the polarizability surface, and on variational wavefunctions considering the rotational-vibrational coupling in full. As a byproduct of this analysis several tables have been compiled including scattering strengths and assignments for individual rotational transitions of the three species. From these tables the Raman spectra in the OH/OD stretching regions can be simulated over the range of temperatures up to 2000 K for H₂O, and up to 300 K for D₂O and HDO.     

Schwingungsspektrum von Magnesiumsulfat-Heptahydrat (Epsomit) und Cäsiumsulfat

As in the preceding paper [1], infrared reflection spectra of single crystals of orthorhombic MgSO₄·7H₂O and MgSO₄·7D₂O have been obtained at 300°K, 80°K, and at about 14°K in the region between 4000 cm^?1 and 400 cm^?1. By a Kronig-Kramers analysis, the frequencies of the infrared active transitions have been determined. The spectra and their temperature dependence are contrasted with reflection spectra of anhydrous, orthorhombic Cs₂SO₄, which show practically no temperature dependence. The spectra of the magnesium compounds show two prominent features: 1. In the region below 700 cm^?1, the low-temperature experiments show the existence of many distinct vibrational modes arising mainly from the coupled translational and librational motions of the water molecules. These observations will be discussed in the light of the results of the preceding paper [1]. 2. The internal vibrations of the SO₄-ions at about 1100 cm^?1 present a very interesting combination of two solid-state effects on vibrational states of molecules in crystals: a) The threefold degeneracy of this mode is lifted by the deformation of the molecule due to the asymmetric crystal field, and b) the coupling of four molecules in the unit cell (resonance or correlation-field coupling) results in a further splitting of each mode into four clearly separated states of which three are infrared active. The magnitude of this splitting is calculated with the Davydov-theory (Coulomb-interaction of the transition-dipoles), making use of the crystal structure and the experimentally determined strength of the transition dipoles. Considering the limitation of the model, fairly good agreement with the experiment is obtained.     

12C(12C, 8Be)16O angular distributions and excitation functions between 35 and 69 MeV bombarding energy

An array of eight detectors has been developed for identifying the particle unstable ⁸Be nucleus from nuclear reactions with high detection efficiency. Absolute cross sections have been measured for the reaction ¹²C(¹²C, ⁸Be_g.s.)¹⁶O to the ground state and to several excited states in ¹⁶O. Excitation functions at seven angles from 15° to 45° (lab) in 5° steps have been measured for bombarding energies between E¹²_C(lab) = 35 and 69 MeV. Excitation functions were obtained for the following states in the residual nucleus ¹⁶O which were found to be strongly populated: g.s.(0⁺); 6.1 MeV (0⁺, 3^?); 6.9 MeV (2⁺); 10.4 MeV (4⁺); 11.1 MeV (4⁺); 14.7 MeV (6⁺,…) and 16.3 MeV (6⁺,…). The energy range is covered in 250 keV (c.m.) steps; at certain energy ranges in ¹²⁵ keV or 50keV steps. All excitation functions exhibit a strong energy dependence of the cross section; pronounced gross structures with superimposed fine structures, similar to those observed for ¹²C+¹²C elastic and inelastic scattering at these energies, are observed. At 19.3 MeV, where resonant structures were observed in the reactions ¹²C(¹²C, p)²³Na, ¹²C(¹²C, n)²³Mg and ¹²C(¹²C, d)²²Na, no resonance is found for the reaction studied here. At 60, 61 and 63 MeV angular distributions have been measured in 1° and 2.5°(lab) angular steps. The excitation functions have been analyzed in terms of Ericson fluctuations and cross-correlation functions.     

Hydrogen bond studies

The deuteron magnetic resonance spectra from partially deuterated single crystals of NaHC₂O₄. H₂O have been studied. The quadrupole coupling tensors for stationary deuterons are determined at about 25°C. The quadrupole coupling constants and the assymmetry parameters η of the tensors for the two deuterons in the water molecule are, 235·2 ± 1·9 and 228·5 ± 1·6 kHz, and 0·09 ± 0·01 and 0·13 ± 0·01, respectively. The principal axes corresponding to the largest components both deviate by 0·9 ± 0·5° from their respective O-H directions. For one of the tensors this angular displacement is in the plane of the H₂O molecule and towards the other O-H direction. The displacement for the other tensor is out of the plane of the H₂O molecule.     

Absolute quantum yields of Cr3+2E → 4A2 emission in solids

The absolute quantum yields of powders have been obtained. The correction factors involved in using this method are described. The room temperature yield of ruby, 0.63 (⁴T₂←⁴A₂ excitation), is in good agreement with the previously reported single crystal results. No change in ruby quantum yield accompanies temperature reduction to 80°K. The absolute quantum yields of dilute (1–2%) Cr³⁺ in NaMgAl (C₂O₄)₃?9H₂O powders are 0.27 at 80°K. A small but measurable concentration dependence is observed with this system. Evidence to support an intramolecular intersystem crossing efficiency of unity is presented.     

Vibrational study of phase transitions and conductivity mechanism in H3OUO2PO4.3 H2O (HUP)

Infrared and Raman spectra of polycrystalline H₃OUO₂PO₄.3 H₂O (HUP) have been envestigated at various temperatures between 50 K and 300 K. The most temperature sensitive bands corresponding to PO₄ and H₂O librations, U-OPO₃ stretching and OH stretching vibrations indicate four different phases of HUP and allow to propose a phase transition mechanism from a quasiliquid state of protonated species in R.T. phase to a fully ordered crystal below 100 K. Protonic conductivity mechanism of room and low temperature phases is discussed.     

The infrared spectrum of OH-compensated defect sites in C-doped MgO and CaO single crystals

The IR spectra of OH-compensated point defects in MgO (and CaO) single crystals of various purity grades were reinvestigated. Three distinct groups of IR bands appear in the O-H stretching region: A, B and C around 3550 cm^?1 (3650 cm^?1), 3300 cm^?1 (3450 cm^?1) and 3700cm^?1 (3750cm^?1). They are assigned as follows: band A to the fully compensated, band B to the half compensated and band C to the overcompensated cation vacancies, [O?V”_catH?]^×, [O?V”_cat], and [O?O?V”_catH?$\text{]}\text{?}$, respectively.Upon cooling to 80 K the band A shows a complex behavior partly due to the formation of Ha molecules by charge transfer and concommittant O^? formation: [? (H₂)”_cat?]^×. The O^? represent defect electrons or positive holes in the O^2? matrix.Bands A and B show a characteristic multiplet splitting which is caused by local lattice strains coming from carbon atoms on near-by interstitial position. The intensity ratios between the multiplet components remain constant regardless of temperature pretreatments up to 1470 K, but strong variations of the integral intensities are observed. These are caused by the highly mobile C atoms entering and leaving reversibly the cation vacancy sites as a function of temperature and of the quenching speed. When the C atoms push the H₂ molecules onto interstitial sites, an H-H stretching signal appears around 4150cm^?1.     

Vibrational study of H3OUO2PO4 · 3 H2O (HUP) and related compounds. phase transitions and conductivity mechanisms: part I,KUO2PO4 · 3 H2O (KUP)

Infrared and Raman spectra of polycrystalline KUO₂PO₄ · 3 H₂O (KUP) and its isotopic derivatives KUO₂P¹⁸O₄ · 3 H₂O and KUO₂PO₄ · 3 D₂O have been investigated in the 4000-10-cm^?1 range at different temperatures. An assignment of the bands in terms of UO₂, PO₄ and H₂O vibrations has been proposed. Combined differential scanning calorimetry and spectroscopic data show two diffuse phase transitions near 130 and 230 K. Comparison of the vibrational spectra of phase I at 300 K and phase IV at 100 K indicates that ordering of the water molecules with subsequent ordering of PO₄ tetrahedra on a site with lower symmetry appears to be the main mechanism responsible for the phase transformation. All the six O-H distances of water molecules in phase IV are found to be crystallographically nonequivalent. Conducting ion frequencies and the corresponding force constants have been determined for the analogous compounds MUP with M = K⁺, Na⁺, Ag⁺, NH⁺₄, Tl⁺ and H₃O⁺ and compared with other properties of these ionic conductors. Conductivity mechanisms in these materials are discussed.     

Anomalous temperature dependence of the paramagnetic resonance line in FeF3 · 3H2O

Anomalous line-broadening in the paramagnetic resonance of FeF₃ · 3H₂O, which has a linear chain arrangement, has been observed. The line width was found to decrease monotonically with increasing temperature in the range from 100–300°K.     

Optical investigation of ErFeO3

The absorption spectrum of single crystals of ErFeO₃ has been investigated in the red and near infrared spectral region in the temperature range between 1.2 °K and 4.2 °K and at 20 °K and 77 °K. Between 77 °K and 4.2 °K a constant splitting of the absorption lines is observed. Below the Néel-temperature of the erbium sublattice at 4.5 °K the splitting of the absorption lines increases; the saturation value extrapolated to 0 °K of the splitting of the lowest crystal field level of the⁴ I _15/2 groundterm is (6.08±0.30) cm^?1. By measuring the Zeeman effect the groundstate magnetic moment is determined asμ=(6.6±0.2)μ _B. The measured temperature dependence of the splitting of the lowest crystalfield level of the⁴I_15/2 groundterm is compared with that calculated by a Monte Carlo method.     

Observation of electromagnetic resonances in crystals of K2Pt (CN)4 Br0.3.3H2O at microwave frequencies

Electromagnetic dielectric resonances in the range 8–11 GHz have been observed in millimeter sized crystals of K₂Pt(CN)₄Br_0.3.3H₂O. This observation results directly from the existence of large dielectric constants; values for the longitudinal and transverse dielectric constants at 4°K are estimated to be ?6 >～ 3000 and ?⊥ ?4.     

IR absorption in p-type pb0.97Sn0.03Se

IR absorption in p-type melt grown Pb_0.97Sn_0.03Se crystals is reported. The results for the room temperature absorption coefficient (α) in the wavelength region 2–15 μm are analysed. The indirect absorption edge is found to be at 0.26 eV for this ternary alloy. In the longwavelength region α is found to be proportional to λ², in agreement with the classical free carrier absorption expression. The conductivity effective mass of holes is found to be 0.067 m₀ at 300°K.