Growth, microhardness, dielectric and photoconductivity characterization of a highly polarizable NLO material: Sodium p-nitrophenolate dihydrate (NO2-C6H4-ONa.2H2O)

Sodium p-nitrophenolate dihydrate (NPNa.2H₂O) is a highly polarisable non linear optical material. It has a d_eff about 1.45 times than that of potassium titanyl phosphate. Single crystals of (NPNa.2H₂O) have been grown successfully by slow solvent evaporation having water and methanol as solvent. The structure of the crystal is verified by single X-ray analysis. Optical absorption shows that the crystal is highly transparent between 1500 and 300 nm. Microhardness of the crystal is found to increases with increase in load and the hardness number is found to be high for methanol grown crystal as compared to the water grown crystal. Electrical conductivity as evaluated from the cole-cole plot is found to be 1.26 × 10⁻⁵ mho m⁻¹. The dielectric constant of the crystal is low and independent at higher frequencies. The crystal has prominent photoconduction in the presence of trap energy levels formed by the Na⁺ ions. The SHG efficiency of the crystal is studied by performing Kurtz powder test and the results of scanning electron microscope analysis indicate that the major part of the crystal surface is free from inclusion and dislocation.     

Study of hopeite coatings: II. Study of polycationic hopeites: structure and dehydration process

The structures and the dehydration processes of phosphates, formed on galvanized steel sheets treated in polycationic solutions containing Zn²⁺, Ni²⁺ and Mn²⁺ as dihydrogenophosphates, are studied using differential and gravimetric thermal analysis (DTA, TGA), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The compounds constituting the phosphated layers, and the crystals precipitated in a stove at 70° C from the same solutions, are structurally substituted-hopeites, (Zn, Mn, Ni)₂(PO₄)₂·4H₂O. Their thermal behaviour is strongly influenced by the presence of Ni²⁺ and Mn²⁺ ions. The dihydrate (Zn₃(PO₄)₂·2H₂O), whose structure conformation has been determined at first, is identified as the main component in the dehydration products of these compounds. The knowledge of the dihydrate conformation allows the understanding of the specificity of the dehydration processes of substituted hopeites whose transformation temperatures and dehydration modes depend on the nature of the substituting cations.     

Study of the luminescence of H2O and D2O ices induced by charged-particle bombardment

We measured the optical emission of H₂O and D₂O ices in visible region (300-500 nm) induced by energetic hydrogen ions (H⁺, H₂⁺, and H₃⁺) irradiation. Our analysis of the data of ion-stimulated luminescence (ISL) shows that all spectra of ISL emission are identical, independent of projectile. We show that all lines in the ISL emission spectrum may be assigned to decays from excited particles and/or fragments of H, H₂, OH, and H₂O. From the independence of emission spectrum on projectile we conclude that the final process causing the emissions may be attributed to the interaction between H⁺ (and/or H) and the water molecules.     

High resolution pure rotational spectrum of water vapor enriched by H217O and H218O

The pure rotational spectrum of a mixture of H₂¹⁶O, H₂¹⁷O and H₂¹⁸O between 50 and 730 cm^?1 was recorded on the Fourier transform spectrometer at the University of Oulu. The resolution achieved was about 0.010 cm^?1 and the precision of the unblended lines was better than 0.001 cm^?1. About 1100 lines were assigned. The measured line positions of H₂¹⁷O and H₂¹⁸O were compared with the values derived from the rotation and distortion constants given in the literature.     

A High Resolution Luminescence Study of two Novel Salts of the Triethvlenetetraaminehexaacetatoeuropate(III) Anion

A low-temperature high-resolution luminescence study of K₃Eu(TTHA)·H₂O and T1₃Eu(TTHA) ·H₂O has been carried out. the Eu³⁺ luminescence spectrum was recorded over the spectral range which includes transitions from the ⁵D₀ excited state to the ⁷F_0-4 ground state manifolds. the observed spectral patterns are analyzed using group theoretical methods so as to deduce the site symmetry of the Eu³⁺ ion in the complex. the analysis shows that the Eu³⁺ ion occupies a spectroscopic site symmetry that approaches a D₂ symmetry with distortion towards a C₂ or lower symmetry in the potassium salt and a site symmetry of a C₃ in the thallium salt. These salts illustrate the potential of the counterion to markedly influence the effective site symmetry of the Eu³⁺ ion.     

Cavity ring-down spectroscopy of H2O in the range 16 570-17 125 cm

Following previous investigations on H₂¹⁶O and H₂¹⁸O by cavity ring-down spectroscopy, this method has now been applied to investigate the energy region of the 5ν polyad in the absorption spectrum of H₂¹⁷O. In the range 16 570-17 125 cm⁻¹, the highest energy range investigated for the H₂¹⁷O isotopologue so far, 516 lines are attributed to H₂¹⁷O and assigned from a newly generated line list.     

Experimental and theoretical study of the ν(HF) absorption band structure in the H2O…HF complex

The νHF absorption band shape of the H₂O…HF complex is studied in the gas phase at a temperature of 293 K. The spectra of H₂O/HF gaseous mixtures in the range 4000–3400 cm^?1 are recorded at a resolution of 0.2–0.02 cm^?1 with Bruker IFS-113v and Bruker IFS-120 HR vacuum Fourier spectrometers in a 20-cm cell. The spectra of the H₂O…HF complex in the region of the ν₁(HF) absorption band are obtained by subtracting the calculated spectra of free H₂O and HF molecules from the experimental spectrum. The ν₁ band of the H₂O…HF complex has an asymmetric shape with a low-frequency head, an extended high-frequency wing, and a characteristic vibrational structure. Two approaches are used to calculate the ν1 band shape as a superposition of rovibrational bands of the fundamental and hot transitions involving the low-frequency modes of the complex. The first approach is based on a simplified semiempirical procedure. The second approach relies on a nonempirical anharmonic calculation of the vibrational energy levels, the frequencies and intensities of the corresponding transitions, and the rotational constants. These parameters are obtained by calculating ab initio the potential energy and dipole moment surfaces in the second-order Möller-Plesset approximation and using the variational method to solve one-, two-, and three-dimensional anharmonic vibrational problems. The absorption spectrum of the complex in the range 3600–3720 cm^?1, reconstructed using the nonempirical electro-optical parameters, reproduces rather well the main features of the experimental spectrum, including the relative intensities of peaks of the vibrational structure. However, the interpretation of most of the structural features of the spectrum differs from that adopted in the semiempirical scheme. First of all, it follows from the results of nonempirical calculation that the central, most intense, maximum of the experimental spectrum should correspond to the v ₁=1←0 transition from the ground vibrational state. This fact gives rise to a new value of the vibrational transition frequency ν ₁ ⁰ in the H₂O…HF complex equal to 3635 cm^?1, which is higher than the commonly accepted value of 3608 cm^?1.     

Raman spectroscopy of hydrogen‐arsenate group (AsO3OH) in solid‐state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2·H2O

Raman spectrum of burgessite, Co₂(H₂O)₄[AsO₃OH]₂· H₂O, was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO₃) and As‐OH units, as well as the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O H···O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO₃OH)²⁻ units in the crystal structure of burgessite was proved, which is in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison. Copyright © 2010 John Wiley & Sons, Ltd.     

High sensitivity ICLAS of H2O in the 12,580-13,550 cm transparency window

High-sensitivity Intracavity Laser Absorption Spectroscopy (ICLAS) is used to measure the high resolution absorption spectrum of H₂¹⁸O between 12,580 and 13,550 cm⁻¹. This spectral region covers the 3v+δ polyad of very weak absorption. Four isotopologues of water (H₂¹⁸O, H₂¹⁶O, H₂¹⁷O, HD¹⁸O) are found to contribute to the observed spectrum. Spectrum analysis is performed with the aid of variational calculations and allowed for assigning 1126 lines belonging to H₂¹⁸O, while only 160 H₂¹⁸O lines are included in the HITRAN-2008 database. Altogether, 823 accurate energy levels of H₂¹⁸O are determined from transitions attributed to 26 upper vibrational states, 438 of them being reported for the first time. New information includes energy levels of four newly observed vibrational states of H₂¹⁸O: (2 4 0), (1 4 1), (0 4 2) and (2 3 1) at 13,167.718, 13,212.678, 13,403.71 and 15,073.975 cm⁻¹, respectively. H₂¹⁸O transitions involving highly excited bending states like (1 6 0), (0 6 1), (0 7 1), (1 7 0), (0 9 0) and even (0 10 0) have been identified as a result of an intensity borrowing from stronger bands via high-order resonance interactions. Thirty-six new energy levels of H₂¹⁷O, present with a 2% relative concentration in our sample, could be determined. The rotational structure of the (0 2 3) state of HD¹⁸O at 13,245.497 cm⁻¹ is also reported for the first time.     

High sensitivity CW-cavity ring down spectroscopy of water in the region of the 1.5 μm atmospheric window

The absorption spectrum of natural water vapour around 1.5 μm has been recorded with a typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹ by using a CW-cavity ring down spectroscopy set up based on fibred DFB lasers. A series of 31 DFB lasers has allowed a full coverage of the 6130.8-6748.5 cm⁻¹ (1.63-1.48 μm) region corresponding to the H transparency band of the atmosphere. The line parameters (wavenumber and intensity) of a total of 5190 lines, including 4247 lines of water vapor, were derived by a one by one fit of the lines to a Voigt profile. Different isotopologues of water (H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O) present in natural abundance in the sample contribute to the spectrum. For the main isotopologue, H₂¹⁶O, 2130 lines were measured with line intensities as weak as 10⁻²⁹ cm/molecule while only 926 lines (including a proportion of 30% inaccurate calculated lines) with a minimum intensity of 3 × 10⁻²⁷ cm/molecule are provided by the HITRAN and GEISA databases. Our comparison in the whole 5750-7965 cm⁻¹ region, has also evidenced that an error in the process of conversion of the intensity units from cm⁻²/atm to cm⁻¹/(molecule × cm⁻²) at 296 K, has led to H₂¹⁶O line intensities values listed in the HITRAN-2000 database, systematically 8 % below the original FTS values. The rovibrational assignment was performed on the basis of the ab initio calculations by Schwenke and Partridge with a subsequent refinement and validation using the Ritz combination principle together with all previously measured water transitions relevant to this study. This procedure allowed determining 172, 139, 71, and 115 new energy levels for the H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O isotopologues, respectively. The results are compared with the available databases and discussed in regard of previous investigations by Fourier transform spectroscopy. The spectrum analysis has showed that most of the transitions which cannot be assigned to water are very weak and are due to impurities such as carbon dioxide and ammonia, leaving only about 3% of the observed transitions unassigned. The interest of a detailed knowledge of water absorption for trace detectors developed in the 1.5 μm range is underlined: for instance HDO contributes significantly to the considered spectrum while no HDO line parameters are provided by the HITRAN database.     

E.P.R. study of Mn2+ in lithium potassium tartrate (LPT) and its isomorphism with lithium ammonium tartrate (LAT)

An E.P.R. study of Mn²⁺ in single crystals of LiKC₄H₄O₆. H₂O (LPT) was carried out from ～300 K to 77 K and four magnetically differently oriented but symmetry related triclinic complexes of Mn²⁺ were observed. Spin hamiltonian parameters were obtained at ～ 300 K. The E.P.R. results suggest that LPT is not only isomorphous but also isostructural to LiNH₄C₄H₄O₆ . H₂O (LAT). In LPT no structural phase transition could be detected in the temperature range 300 K to 77 K. The observed small magnitude of the low symmetry effect is attributed to the small contribution of fourth order crystal field terms relative to that of the second order crystal field terms, to the zero-field splittings of the ⁶ S ground state of Mn²⁺. A temperature dependent anomalous behaviour is observed in the low field region of the E.P.R. spectrum for B//[010] and its neighbourhood.     

Photon stimulated ion desorption of H+ ions from GaAs (110)/H2O

The photon stimulated ion desorption yield of H⁺ ions from a H₂O dosed GaAs (110) surface has been measured in the range 18eV ? hυ ? 30eV. There is a direct correspondence between the PSID H⁺ yield, reflectance, and the secondary electron yield spectrum of GaAs (110). The data provides evidence that the initial stages of PSID involve core level (Ga(3d), O(2s)) → conduction band excitation followed by Auger decay.     

Absorption spectrum of deuterated water vapor enriched by 18O between 6000 and 9200 cm−1

The absorption spectrum of water vapor enriched by deuterium and oxygen-18 is analyzed in the 6000–9200 cm^?1 region. The spectrum has been recorded at room temperature with a Bruker IFS 120 h Fourier transform spectrometer. More than 14,000 absorption lines were measured in the recorded spectrum. The vibration–rotation assignments were performed on the basis of previously published experimental energies and of variational calculations. Nine water species (H₂¹⁶O, HD¹⁶O, D₂¹⁶O, H₂¹⁸O, HD¹⁸O, D₂¹⁸O, H₂¹⁷O, HD¹⁷O and D₂¹⁷O) were found to contribute to the observed absorption. More than 3600 lines of 19 vibrational bands of D₂¹⁸O and about 4700 lines of 16 bands of HD¹⁸O with J as high as 19 and K_a as high as 11 were assigned. The main part of the HD¹⁸O and D₂¹⁸O lines and all lines of HD¹⁷O and D₂¹⁷O were observed in the laboratory for the first time. The obtained vibration–rotation energy levels are compared with previous experimental studies and the results of variational calculations.     

Linear and nonlinear optical properties of yttrium formate dihydrate,Y(HCOO)<Subscript>3</Subscript>·2H<Subscript>2</Subscript>O

Yttrium formate dihydrate, Y(HCOO)₃·2H₂O (point group 222), a promising new material for Raman laser frequency converters, has been reinvestigated with respect to the linear and nonlinear optical (second-harmonic generation, SHG) properties. High-precision data of refractive indices and their dispersion in the wavelength range 365–1083 nm are given, together with the three independent components of the tensor of nonlinear optical susceptibility (SHG) [d_ijk ^SHG]. A calculation of the macroscopic nonlinear optical susceptibility from the hyperpolarizabilities of the formate groups results in good agreement with the experimental values. This signals that the nonlinear optical interaction in Y(HCOO)₃·2H₂O can mainly be attributed to the formate groups. PACS 42.65.Ky; 42.70.Mp; 78.20.Ci     

EPR studies on aqueous sucrose solutions using (Cu(H2O)6)2+ spin probe

EPR investigations using Cu²⁺ ion as a probe have been performed on supersaturated sucrose solution with percent concentration c = 66 as a function of temperature T, and at room temperature as a function of c. The motionally averaged spectrum of [Cu(H₂O)₆]²⁺ was used to monitor the changes in intermolecular interactions that occur as a function of [c, T]. A drastic increase in the line width, symptomatic of increase in the rotational correlation time of [Cu(H₂O)₆]²⁺, is observed between 293 and 288 K. The motionally averaged spectrum disappears below 281 K. The motionally averaged spectrum is also absent in the room temperature spectra of the solution with c= 85. Even in the [c, T] range where [Cu(H₂O)₆]² is found to be nearly static, these molecules appear to have an orientational fluctuation manifesting in the m ₁ dependence of the line width of the parallel component.     

Electronic Spectra and the Mechanism of Complexing of Uranyl Nitrate in Water–Acetone Solutions

Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO₂(NO₃)₂·6H₂O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO₂·5H₂O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO₂(NO₃)₂·2H₂O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given.     

H<Subscript>3</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H₃O ₂ ^- ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H₃O ₂ ^- ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H₃O ₂ ^- ions is demonstrated. The equilibrium concentrations of monohydrate (H₃O ₂ ^- ? H₂O) and dihydrate (H₃O ₂ ^- ? 2H₂O) are calculated and their IR continuous absorption spectra are isolated.     

Chemisorbed phases of H2O on TiO2 and SrTiO3

Ultraviolet photoemission spectroscopy in ultrahigh vacuum has been used to study the interaction of H₂O with argon-ion-bombarded and annealed TiO₂(110) and SrTiO₃ (100) surfaces. At low exposure, evidence is found for the presence of the OH free radical on both bombarded and annealed TiO₂. At high exposure, a spectrum of slightly perturbed adsorbed H₂O is observed, with the a₁ molecular orbital shifted 0.5–1 eV toward tighter binding. This suggests that H₂O binds to the surface of TiO₂ via its a₁, in-plane O lone-pair orbital. No evidence is found for OH on the surface of SrTiO₃. The spectrum of H₂O adsorbed on bombarded SrTiO₃ shows both the a₁ and b₂ molecular orbitals shifted 0.4 toward tighter binding, indicating a more complicated bonding to the surface. For SrTiO₃ that has been bombarded and then annealed, the spectrum of adsorbed H₂O shows no significant bonding effects.     

Absorption spectrum of water as a reflection of charge diffusion

The absorption spectrum of liquid water in the range of 10³–10¹³ Hz (from dc conductivity of up to 5 THz IR resonance) is completely and uniformly described by a simple physical model. The model assumes the existence in water of a high concentration of H₃O⁺ and OH^? ions (up to 4.5% of the total number of molecules) that exchange protons with H₂O molecules on the scale of picoseconds.     

A Raman spectroscopic study of bukovskýite Fe2(AsO4)(SO4)(OH)· 7H2O,a mineral phase with a significant role in arsenic migration

The Raman spectrum of bukovskýite [Fe³⁺₂(OH)(SO₄)(AsO₄)· 7H₂O] has been studied and compared with that of an amorphous gel containing specifically Fe, As and S, which is understood to be an intermediate product in the formation of bukovskýite. The observed bands are assigned to the stretching and bending vibrations of (SO₄)²⁻ and (AsO₄)³⁻ units, stretching and bending vibrations and vibrational modes of hydrogen‐bonded water molecules, stretching and bending vibrations of hydrogen‐bonded (OH)⁻ ions and Fe³⁺ (O,OH) units. The approximate range of O H···O hydrogen bond lengths was inferred from the Raman spectra. Raman spectra of crystalline bukovskýite and of the amorphous gel differ in that the bukovskýite spectrum is more complex, the observed bands are sharp and the degenerate bands of (SO₄)²⁻ and (AsO₄)³⁻ are split and more intense. Lower wavenumbers of δ H₂O bending vibrations in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared to those in bukovskýite. Copyright © 2011 John Wiley & Sons, Ltd.