Electric field gradients in fluoride crystalline powders: correlation of NMR measurements with ab initio calculations

Electric field gradients (EFG) of ²³Na and ²⁷Al in three model fluoride crystalline powders AlF₃, Na₃AlF₆ and Na₅Al₃F₁₄ were computed using the density functional based electronic structure code WIEN97 and compared to values derived from nuclear magnetic resonance (NMR). First, results of measurements of ²³Na and ²⁷Al quadrupolar parameters in AlF₃, Na₃AlF₆ and Na₅Al₃F₁₄ were revisited by using high-resolution solid-state NMR. To determine chemical shifts and quadrupolar parameters with a high precision, the experimental procedure involved magic angle spinning, satellite transition spectroscopy and multi-quanta techniques applied to the quadrupolar nuclei together with a computed reconstruction of the NMR spectra. The large discrepancies which appear between previously published results in some cases, justify the use of ab initio calculations of the corresponding EFG using the WIEN97 code based on the known structural data of the crystalline phases. The agreement obtained between these calculations and the experimental results which is better than 10% in almost all cases supports the reliability of the present NMR investigations and of the crystallographic data.     

Solvent dependent study of carbonyl vibrations of 3‐phenoxybenzaldehyde and 4‐ethoxybenzaldehyde by Raman spectroscopy and ab initio calculations

A Raman spectroscopy investigation of the carbonyl stretching vibrations of 3‐phenoxybenzaldehye (3Phbz) and 4‐ethoxybenzaldeheyde (4Etob) was carried out in binary mixtures with different polar and nonpolar solvents. The purpose of this study was twofold: firstly, to describe the interaction of the carbonyl groups of two solute molecules in terms of a splitting in the isotropic and anisotropic components and secondly, to analyze their spectroscopic signatures in a binary mixture. Changes in wavenumber position, variation in the anisotropic shift and full width half maximum were investigated for binary mixtures with different mole fractions of the reference systems. In binary mixtures, the observed increase in wavenumber with solvent concentration does not show linearity, indicating the significant role of molecular interactions on the occurrence of breaking of the self‐association of the solute. In all the solvents, a gradual decrease in the anisotropic shift reflects the progressive separation of the coupled oscillators with dilution. Γ_i(η_c), 3Phbz—solvent mixtures, exhibit a gradual decrease with decrease in the concentration of the solute which is an evidence on the influence of micro viscosity on linewidth. For 4Etob, the carbonyl stretching vibration shows two well‐resolved components in the Raman spectra, attributed to the presence of two distinct carbonyl groups: hydrogen‐bonded and free carbonyl groups. The intensity ratio of the carbonyl stretching vibration of these two types of carbonyl groups is studied to understand the dynamics of solute/solvent molecules owing to hydrogen bond interactions. Ab initio calculations were employed for predicting relevant molecular structures in the binary mixtures arising from intermolecular interactions, and are related to the experimental results. Copyright © 2009 John Wiley & Sons, Ltd.     

Concentrated Fe(III)–nitrilotriacetate solutions: study by Raman spectroscopy and ab initio calculations

Fe(III)–nitrilotriacetate(NTA) aqueous solutions are used in various redox desulfurization processes. The nature of stable Fe–NTA complexes depends highly on parameters such as [Fe(III)] concentration, NTA/Fe ratio and pH value. These complexes can be characterized by potentiometric measurements or UV‐vis spectroscopy, but only at rather low concentrations. Using synthesis of solids, Raman spectra of these solids and ab initio calculations, a rational determination of the nature of complexes stable in water at high iron concentrations was proposed from the position sensitivity of the main low wavenumber band to the coordination sphere of iron cations. This band was assigned to ν(Fe N) stretching vibrations from ab initio calculations. Depending on the pH and NTA/Fe ratio of the prepared solutions, different species were identified from the Raman spectra. The present methodology can be extended to other metal–ligand systems to elucidate the nature of stable complexes in aqueous solution. Copyright © 2006 John Wiley & Sons, Ltd.     

Formation and decomposition of N‐alkylnaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8‐N‐butyl‐naphthalimide (1,8‐NBN) to 1,8‐N‐butyl‐naphthalamide (1,8‐NBAmide) and of 2,3‐N‐butyl‐naphthalimide (2,3‐NBN) to 2,3‐N‐butyl‐naphthalamide (2,3‐NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8‐NBN equilibrates with 1,8‐NBAmide in mild alkali. Under the same conditions 2,3‐NBN quantitatively yields 2,3‐NBAmide. Over a wide range of acidities the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH's. Anhydride formation in acid was demonstrated for 1,8‐NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six‐membered ring intermediates. The rate of carboxylic acid assisted 1,8‐N‐Butyl‐naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright © 2010 John Wiley & Sons, Ltd.     

Non-random Be-to-Zn substitution in ZnBeSe alloys: Raman scattering and ab initio calculations

We show how the 1-bond ↦ 2-mode percolation behaviour, as observed in the transverse optical (TO) Raman spectra of several A_1-xB_xC semiconductor (SC) alloys, can be used to detect and to estimate a possible deviation from randomness in the A↔B substitution. As a case study we focus on the Zn_1-xBe_xSe system, which shows an uniquely well-resolved percolation-type TO fine structure in the spectral range of Be–Se vibrations, and discuss differences in the Be–Se Raman signals from bulk crystals and epitaxial layers. In the epilayers, the longer (shorter) Be–Se bonds from the BeSe-like (ZnSe-like) region appear to be slightly but systematically over- (sub-) represented with respect to the random case. This indicates a trend towards local ordering in analogy with the known case of InGaP₂. The discussion is supported by ab initio insight into the phonon/bond length properties of a prototype ZnBeSe supercell at x ~ 0.5 in their dependence on the amount of CuPt ordering (the most frequent type of spontaneous ordering). Besides, the ab initio calculations reveal some singularity in the lattice dynamics/relaxation around the intermediate value of the order parameter η ~ 0.5, coinciding with the so far experimentally achievable limit of CuPt spontaneous ordering.     

Local structure of technologically modified g-GeS2: resonant Raman and absorption edge spectroscopy combined with ab initio calculations

We have used resonant Raman and absorption edge spectroscopy together with first-principle calculations in order to study the structure of GeS₂ glasses (g-GeS₂). The glasses were prepared under different melt temperatures and cooling rates, which are shown to significantly influence the g-GeS₂ structure at the nano-scale. The combined use of Raman spectroscopy and ab initio calculations reveals the origin of the molecular level electronic structure and its connection to the interesting technological features of the g-GeS₂. Local structure within the glasses is discussed in terms of atomic Ge _n S _m clusters. The band gaps computed for these clusters and their correlation to the experimental band gaps and the possible formation of band tail states are also discussed.     

Relativistic effects in PtF6 and isoelectronic octahedral groups: Magnetic susceptibility, 19F NMR, and ab initio calculations

The temperature-independent paramagnetism and high O _h symmetry of PtF₆ molecules in solids (at 77 K) and of the octahedral molecular complexes [IrF₆]^? in KIrF₆ and [OsF₆]^2? in K₂OsF₆ are shown to be consistent with the model of strong spin-orbit coupling of 5d ⁴ electrons.     

Metal-substitution strategy to control the conductive path in titanium dioxide: ab initio calculations

Revealing the atomic-nature of the conductive path in TiO₂ layer based resistive-switching devices still remains a critical challenge. Metal atoms doping in TiO₂ layer are always considered as an effective way to improve the electronic properties in resistive random access memory. Efforts to clarify the effects of metal atom substitution on the conductive path in rutile TiO₂ have been done by using first-principles calculation. The dependence of the conductive path on the substitution of Ag/Cu/Al/Hf/Ta/V adjacent to the ordering oxygen vacancies or away from them has been studied in detail to elucidate the formation mechanism of conductive path. Theoretical investigation demonstrates that Hf or V substitution where it occurs adjacent to the oxygen vacancies benefits electrons aggregation among Ti-ions. Such electrons aggregation, which is one type of the conductive path in TiO₂, will be prompted by Ti-t2g orbital electron. The dependent relation of the conductive path on the substitution of Ag/Cu/Al/Hf/Ta/V will be an important factor to optimize future resistive random access memory.     

Local structure investigation of the active site of the imidazolonepropionase from Bacillus subtilis by XANES spectroscopy and ab initio calculations

Imidazolonepropionase is an important enzyme that plays a crucial role in the degradation of the histidine in mammals and bacteria. In this contribution a detailed structural investigation is presented of the imidazolonepropionase from Bacillus subtilis at the zinc site by X‐ray absorption near‐edge structure (XANES) spectroscopy combining experimental data with ab initio calculation in the framework of the multiple‐scattering theory. The resolved local structure leads to a modification of the data set in the Protein Data Bank (PDB) (PDB code 2BB0). Actually, data suggest that the carboxyl of the Asp324 moves far away from the zinc ion at the center, while the water molecule and the nearest‐neighbor histidines move towards it. This new conformation and the occurrence of a short water‐to‐zinc bond length support the nucleophilic attack catalytic mechanism proposed for this enzyme.     

Phonon and electronic properties of the LiCaAlF<Subscript>6</Subscript> crystal: Experiment and ab initio calculations

The results obtained in a cell with a distance between windows on the order of several hundreds of nanometers (the so-called “nanocell”) are presented. The nanocell thickness L in the vertical direction changes from 100 to 900 nm. It is shown that the use of a nanocell with thickness L = λ/2, where λ is a laser wavelength resonant to the atomic transition D2 in sodium atoms, provides sub-Doppler resolution of transmission and fluorescence spectra.     

Atomic displacements and short-range order in the FeSi soft magnetic alloy: Experiment and ab initio calculations

In order to determine the mechanism responsible for the formation of short-range order in dilute FeSi solid solutions, the chemical bonding, atomic displacements near the metalloid, and the enthalpy of silicon dissolution in iron have been studied within density functional theory. It is found that the directed character of the Si-Fe chemical bond formed upon the p-d hybridization brings about an anisotropy in atomic displacements near silicon atoms. Calculations of the Si-Si effective pairwise interaction energy offer an explanation for the observed features in short-range order in FeSi and suggest that ferromagnetic bcc Fe does not have a tendency toward Si atom clusterization. The mechanism of formation of the anisotropy induced by application of an external load or a magnetic field is discussed.     

Direct ab initio dynamics calculations of the reaction rate for the hydrogen abstraction reaction of NCO with CH4 and C2H6

The kinetics of the hydrogen abstraction reactions NCO + CH₄ (R1) and NCO + C₂H₆ (R2) have been studied over a wide temperature range. The minimum energy paths (MEPs) were calculated at the MP2/cc-pVDZ level and single-point calculations were refined at the G3MP2 level. The rate constants for the title reactions were calculated using canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) contributions. The fitted three-parameter formulae are k ₁ = 2.52 × 10^?22 T ^3.46 exp(2466/T) and k ₂ = 9.8 × 10^?22 T ^3.2 exp(411.8/T) cm³ molecule^?1 s^?1 for (R1) and (R2), respectively. The calculated rate constants were found to be in good agreement with the available experimental data. Deuterium kinetic isotope effects were also investigated. Both reactions show a significant kinetic isotope effect in the low-temperature range.     

Determination of the molecular dipole moment of bromofluoromethane: Microwave Stark spectra and ab initio calculations

The electric dipole moment of bromofluoromethane, CH₂⁷⁹BrF, has been determined with a good accuracy by observing the second order ΔM_J = 0 Stark spectrum of the J = 3_2,1 ← 3_1,2, J = 5_2,3 ← 5_1,4 and J = 5_2,4 ← 5_1,5 rotational transitions. In addition, the equilibrium geometry and dipole moment have been evaluated using highly accurate ab initio calculations. By comparing the experimental [μ_a = 0.3466(11) D and μ_b = 1.704(26) D] and theoretical [μ_a = −0.339 D and μ_b = −1.701 D] dipole moment components, a very good agreement has been found.     

Acid assisted proton transfer in 4‐[(4‐R‐phenylimino)methyl]pyridin‐3‐ols: NMR spectroscopy in solution and solid state,X‐ray and UV studies and DFT calculations

The behaviour of Schiff bases of 3‐hydroxy‐4‐pyridincarboxaldehyde and 4‐R‐anilines (R?H, CH₃, OCH₃, Br, Cl, NO₂) in acid media has been described. ¹H, ¹³C, ¹⁵N‐NMR chemical shifts allow to establish the protonation site and its influence on the hydroxyimino/oxoenamino tautomerism. DFT calculations, electronic spectra and X‐ray diffraction are in agreement with the NMR conclusions. Copyright © 2007 John Wiley & Sons, Ltd.     

Millimetre-wave and diode laser spectroscopy of IC 15N: anharmonic force field of cyanogen iodide from spectroscopic data and ab initio calculations

(Molecular Physics, 1998, 93, 95–106)     

Periodic ab initio calculation of nuclear quadrupole parameters as an assignment tool in solid-state NMR spectroscopy: applications to 23Na NMR spectra of crystalline materials

Periodic ab initio HF calculations using the CRYSTAL code have been used to calculate (23)Na NMR quadrupole parameters for a wide range of crystalline sodium compounds including Na(3)OCl. An approach is developed that can be used routinely as an alternative to point-charge modelling schemes for the assignment of distinct lines in (23)Na NMR spectra to specific crystallographic sodium sites. The calculations are based on standard 3-21 G and 6-21 G molecular basis sets and in each case the same modified basis set for sodium is used for all compounds. The general approach is extendable to other quadrupolar nuclei. For the 3-21 G calculations a 1:1 linear correlation between experimental and calculated values of C(Q)((23)Na) is obtained. The 6-21 G calculations, including the addition of d-polarisation functions, give better accuracy in the calculation of eta((23)Na). The sensitivity of eta((23)Na) to hydrogen atom location is shown to be useful in testing the reported hydrogen-bonded structure of Na(2)HPO(4).     

Molecular structure,NMR and vibrational spectral analysis of 2,4‐difluorophenol by ab initio HF and density functional theory

Quantum chemical calculations of energies, geometries and vibrational wavenumbers of 2,4‐difluorophenol (2,4‐DFP) were carried out by using ab initio HF and density functional theory (DFT/B3LYP) methods with 6‐311G(d,p) as basis set. The optimized geometrical parameters obtained by HF and DFT calculations are in good agreement with related molecules. The best level of theory in order to reproduce the experimental wavenumbers is the B3LYP method with the 6‐311G(d,p) basis set. The difference between the observed and scaled wavenumber values of most of the fundamentals is very small. A detailed interpretation of the infrared and Raman spectra of 2,4‐DFP is also reported. The entropy of the title compound was also performed at HF/6‐311G(d,p) and B3LYP/6‐311G(d,p) levels of theory. The isotropic chemical shift computed by ¹H, ¹³C NMR analyses also shows good agreement with experimental observations. The theoretical spectrograms for FT‐IR and FT‐Raman spectra of the title molecule have been constructed. Copyright © 2009 John Wiley & Sons, Ltd.     

The impact of the dopants on the formation of conductive path in titanium dioxide: ab initio calculations

Ab initio calculations are performed about the dependent characteristics of theconductive path on Ti/Cu/Zr interstitials and oxygen vacancies in rutile-type titaniumdioxide. It is found that eight oxygen vacancies in two columns around five Ti-ions couldlead to a conductive path. Besides, the conductive path will occur when additional fouroxygen vacancies exist at the third column in ?110 ? direction rather than on (110) facet. Oxygen vacancies at thethird and fourth columns on (110) facet are considered and lead to a conductive path.Furthermore, one or three metal interstitials, such as Ti, Cu or Zr, are doped in titaniumdioxide with three columns of oxygen vacancies on (110) facet, respectively. Theconductive path is only found in the structure above with three Ti interstitials. Weconclude that more Ti interstitials doping in reduced TiO₂ benefit the formation of stableconductive path in resistive random access memory.     

Conformational and structural studies of n‐propylamine from temperature dependent Raman and far infrared spectra of xenon solutions and ab initio calculations

The Raman and infrared spectra (4000 to 50 cm^–1) of the gas, liquid or solution, and solid have been recorded of n‐propylamine, CH₃CH₂CH₂NH₂. Variable temperature (−60 to −100 °C) studies of the Raman (1175 to 625 cm^–1) and far infrared (600 to 10 cm^–1) spectra dissolved in liquid xenon were carried out. From these data, the five possible conformers were identified and their relative stabilities obtained with enthalpy difference relative to trans–trans (Tt) for trans–gauche (Tg) of 79 ± 9 cm^–1 (0.9 ± 0.1 kJ/mol); for Gg of 91 ± 26 cm^–1 (1.08 ± 0.3 kJ/mol); for Gg′ of 135 ± 21 cm^–1 (1.61 ± 0.2 kJ/mol); for Gt of 143 ± 11 cm^–1 (1.71 ± 0.1 kJ/mol). The percentage of the five conformers is estimated to be 18% for the Tt, 24 ± 1% for Tg, 23 ± 3% for Gg, 18 ± 1% for Gg′ and 18 ± 1% for Gt at ambient temperature. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ from both second‐order Møller–Plesset (MP2, full) and density functional theory calculations by the Becke, three‐parameter, Lee–Yang–Parr method. Vibrational assignments were provided for the observed bands for all five conformers, which are supported by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2012 John Wiley & Sons, Ltd.