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Atomic Orbitals (atomic + orbital)
Selected AbstractsThe 15N-CPMAS spectra of simazine and its metabolites: measurements and quantum chemical calculationsEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 4 2007A. E. Berns Summary DFT calculations are a powerful tool to support NMR studies of xenobiotics such as decomposition studies in soil. They can help interpret spectra of bound residues, for example, by predicting shifts for possible model bonds. The described bound-residue models supported the hypothesis of a free amino side chain already suspected by comparison with the experimental data of the standards. No match was found between the calculated shifts of amide bondings of the amino side chains (free or substituted) and the experimental NMR shifts of a previous study. In the present paper, first-principles quantum chemical calculations were used to support and check the interpretation of the 15N cross polarization-magic angle spinning nuclear magnetic resonance (15N-CPMAS NMR) spectra of simazine and its metabolites. Density functional theory (DFT) calculations were performed using Gaussian 03 and the nuclear magnetic shielding tensors were calculated using the Gauge-Independent Atomic Orbital (GIAO) method and B3LYP/6,311+G(2d,p) model chemistry. Good agreement was reached between the calculated and measured chemical shifts of the core nitrogens and the lactam and lactim forms of the hydroxylated metabolites could be clearly distinguished. The calculated spectra showed that these metabolites exist preferentially in the lactam form, an important fact when considering the possible interactions of such hydroxylated metabolites with the soil matrix. Although the calculated bound-residue models in the present study only partly matched the experimental data, they were nevertheless useful in helping to interpret the experimental NMR results of a previous study. To get a better match between the calculated and the measured shifts of the side-chain nitrogens the calculations need to be further developed, taking into account the influence of neighbouring molecules in the solid state. Altogether, quantum chemical calculations are very helpful in the interpretation of NMR spectra. In the future, they can also be very useful for the prediction of NMR shifts, in particular when it is not possible to measure the metabolites due to a lack of material or in cases where practical experiments cannot be conducted. [source] AIM and NBO analysisMAGNETIC RESONANCE IN CHEMISTRY, Issue 9 2010In the series of diaminoenones, large high-frequency shifts of the 1H NMR of the NH group in the cis -position relative to the carbonyl group suggests strong NH···O intramolecular hydrogen bonding comprising a six-membered chelate ring. The NH···O hydrogen bond causes an increase of the 1J(N,H) coupling constant by 2,4 Hz and high-frequency shift of the 15N signal by 9,10 ppm despite of the lengthening of the relevant NH bond. These experimental trends are substantiated by gauge-independent atomic orbital and density functional theory calculations of the shielding and coupling constants in the 3,3-bis(isopropylamino)-1-(aryl)prop-2-en-1-one (12) for conformations with the Z - and E -orientations of the carbonyl group relative to the NH group. The effects of the NH···O hydrogen-bond on the NMR parameters are analyzed with the atoms-in-molecules (AIM) and natural bond orbital (NBO) methods. The AIM method indicates a weakening of the NH···O hydrogen bond as compared with that of 1,1-di(pyrrol-2-yl)-2-formylethene (13) where NH···O hydrogen bridge establishes a seven-membered chelate ring, and the corresponding 1J(N,H) coupling constant decreases. The NBO method reveals that the LP(O) ,,*NH hyperconjugative interaction is weakened on going from the six-membered chelate ring to the seven-membered one due to a more bent hydrogen bond in the former case. A dominating effect of the NH bond rehybridization, owing to an electrostatic term in the hydrogen bonding, seems to provide an increase of the 1J(N,H) value as a consequence of the NH···O hydrogen bonding in the studied diaminoenones. Copyright © 2010 John Wiley & Sons, Ltd. [source] DFT-GIAO1H NMR chemical shifts prediction for the spectral assignment and conformational analysis of the anticholinergic drugs (,)-scopolamine and (,)-hyoscyamineMAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2010Marcelo A. Muñoz Abstract The relatively large chemical shift differences observed in the 1H NMR spectra of the anticholinergic drugs (,)-scopolamine 1 and (,)-hyoscyamine 2 measured in CDCl3 are explained using a combination of systematic/molecular mechanics force field (MMFF) conformational searches and gas-phase density functional theory (DFT) single point calculations, geometry optimizations and chemical shift calculations within the gauge including/invariant atomic orbital (GIAO) approximation. These calculations show that both molecules prefer a compact conformation in which the phenyl ring of the tropic ester is positioned under the tropane bicycle, clearly suggesting that the chemical shift differences are produced by the anisotropic effect of the aromatic ring. As the calculations fairly well predict these experimental differences, diastereotopic NMR signal assignments for the two studied molecules are proposed. In addition, a cursory inspection of the published 1H and 13C NMR spectra of different forms of 1 and 2 in solution reveals that most of them show these diastereotopic chemical shift differences, strongly suggesting a preference for the compact conformation quite independent of the organic or aqueous nature of the solvent. Copyright © 2010 John Wiley & Sons, Ltd. [source] X-ray atomic orbital analysis of 4f and 5d electron configuration of SmB6 at 100, 165, 230 and 298,KACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2010Shiro Funahashi Accurate electron-density measurement of SmB6 at 100, 165, 230 and 298,K, and X-ray atomic orbital (XAO) analysis were carried out. The 4f -electron density around Sm and 5d electron density at ,,1,Å from Sm were analysed by XAO analysis. The 5d electron density is due to the electrons of the 5dJ = 5/2,8 orbitals which stem from the eg orbitals in the strong field approximation. The change in electron populations of the 5d5/2,8 orbitals with temperature is similar to that of the resistivity. Since the conduction band consists of 5d5/2,8 and B-2p orbitals according to band theory, this indicates that the larger populations of the 5d5/2,8 orbitals correspond to the larger number of localized electrons and are correlated to the resistivity of SmB6. The occupation of the bulky 5d5/2,8 orbitals may be the reason for the elongation of the lattice parameter below 150,K. The 4f7/2,6 orbitals are obviously occupied except at 100,K, which seems to be caused by the energy gap between 4f5/2 and 4f7/2 states, which begins to exist between 100 and 150,K, and may represent one of the properties of a Kondo insulator. [source] 5d and 4f electron configuration of CeB6 at 340 and 535,KACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2008Ryoko Makita X-ray atomic orbital (XAO) analysis revealed that at both temperatures the electrons are transferred from B 2px(= py) to Ce 5d and 4f orbitals. At 340,K 5d(j = 5/2),8 orbitals are occupied partially, but 4f(j = 5/2),8 orbitals are more populated than 4f(j = 5/2),7 orbitals, in contrast to our observation at 430,K [Makita et al. (2007). Acta Cryst. B63, 683,692]. At 535,K the XAO analysis revealed clearly that the order of the energy levels of 4f(j = 5/2),8 and ,7 states reversed again and is the same as that at room temperature. It also limited the possible 5d configurations to three models among the nine possible ones. However, the XAO analysis could not decide which of the three models was the best with the present accuracy of the measurement. Two of them have partially and fully occupied 5d(j = 5/2),7 orbitals and the remaining one has a fully occupied 5d(j = 3/2),8 orbital. Since the lobes of 5d(j = 3/2),8 or 5d(j = 5/2),7 orbitals do not overlap with the 4f(j = 5/2),8 orbitals as well as the 5d(j = 5/2),8 orbitals, the order of the energy levels of the 4f(j = 5/2) orbitals became the same as that at room temperature. These results indicate that the crystal field varies with temperature due to the electron transfer from B 2p to Ce 5d orbitals. The difference densities after the spherical-atom refinement at the three temperatures clearly revealed the different combinations of 4f and 5d orbitals which are occupied. In the present study positive peaks due to the 4f electrons appear near the Ce nucleus and those due to 5d orbitals are found in the area outside the 4f peaks. Between the two areas there is a negative area distributed spherically at 340,K. The negative area produced by the contraction of 4f(j = 5/2),8 orbitals seems to reduce the electron repulsion of the 5d(j = 5/2),8 orbitals and helps the 4f(j = 5/2),8 orbitals to remain as the ground state. [source] General two-electron exponential type orbital integrals in polyatomics without orbital translations,INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2009Philip E. Hoggan Abstract This article advocates the use of atomic orbitals which have direct physical interpretation, i.e., hydrogen-like orbitals. They are exponential type orbitals (ETOs). Convenient nodeless linear combinations are used, namely Slater type orbitals (STOs) (with a product of a single power of r and an exponential as radial factor). Until 2008, such orbital products on different atoms were difficult to manipulate for the evaluation of two-electron integrals. The difficulty was mostly due to cumbersome orbital translations involving slowly convergent infinite sums. These are completely eliminated using Coulomb resolutions. They provide an excellent approximation that reduces these integrals to a sum of one-electron overlap-like integral products that each involve orbitals on at most two centers. Such two-center integrals are separable in prolate spheroidal coordinates. They are thus readily evaluated. Only these integrals need to be re-evaluated to change basis functions. The above is still valid or three-center integrals. In four-center integrals, the resolutions require translating one potential term per product. This is outlined here and detailed elsewhere. Numerical results are reported for the H2 dimer and CH3F molecule. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Periodic models in quantum chemical simulations of F centers in crystalline metal oxidesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2007Yuri F. Zhukovskii Abstract We present a survey of recent first principles simulations of the neutral oxygen vacancies (F centers) existing as native or radiation-induced point defects in various crystalline metal oxides in different forms (bulk, bare substrate surface, and on the interface with metal adsorbates). We mainly consider periodic models in calculations of point defects using the metal oxide supercell or cyclic clusters. We compare different formalisms of first principles calculations, mostly the Density Functional Theory (DFT) as implemented in the framework of either localized basis set of atomic orbitals or delocalized basis sets of plane waves. We analyze in detail the structural and electronic properties of F centers in binary oxides of light metals (MgO and Al2O3), and ternary metal oxides (SrTiO3, BaTiO3, PbTiO3, KNbO3, and PbZrO3 perovskites). When available, we compare results of ab initio periodic defect calculations with experimental data, results of the first principles cluster calculations (both embedded and molecular) as well as with semi-empirical calculations. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] Ab initio calculations and analysis of chemical bonding in SrTiO3 and SrZrO3 cubic crystalsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2006R. A. Evarestov Abstract The possibility of the different first-principles methods to describe the chemical bonding in SrTiO3 and SrZrO3 cubic crystals is investigated. The local properties of the electronic structure (atomic charges, bond orders, atomic delocalization indexes, and polarization fractions) were calculated with different methods: traditional Mulliken population analysis in LCAO calculations, two projection techniques in plane-wave (PW) calculations, population analysis based on Wannier-type atomic orbitals, and chemical bonding analysis based on the localized Wannier functions for occupied (valence band) LCAO states. All the techniques considered except the traditional Mulliken analysis demonstrate that the ionicity of chemical bonding in SrZrO3 is larger than in SrTiO3, in agreement with the Zr and Ti electronegativities relation and the relative bandgaps observed. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Local characteristics of the electronic structure of MgO: LCAO and plane-wave calculationsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 2 2005R. A. Evarestov Abstract Linear combinations of atomic orbitals and plane-wave calculations of the electronic structure of the ionic crystal MgO were performed. Local characteristics of the electronic structure of this crystal are obtained using the traditional approaches and the method based on Wannier-type atomic orbitals (WTAOs). It is demonstrated that the results of the conventional methods for chemical bonding analysis in MgO are contradictory and unreasonable. On the contrary, the results of the WTAO method for both types of the basis correctly exhibit the ionic nature of chemical bonding in this crystal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Computation on symmetry-invariant basesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2003Jian Wu Abstract There is standard methodology available to facilitate electronic structure computations on a space that is invariant under a symmetry group. Here, we focus on additional consequences that arise if the basis itself is invariant under the symmetry group (i.e., in the case that application of symmetry operations to each basis vector yields, up to proportionality, a single basis vector). In illustration of the formal development, examples are considered where the symmetries are point-group symmetries and the basis vectors are Slater determinants over singly occupied atomic orbitals, as for an open-shell valence bond (VB) model. Several other types of examples are mentioned, e.g., a basis of chemically motivated resonance structures, as for a VB model, or an orbital basis of atomic orbitals for a one-electron Hückel-type model. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 7,22, 2003 [source] Modified regional self-interaction corrected time-dependent density functional theory for core excited-state calculationsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 16 2009Ayako Nakata Abstract A modified regional self-interaction correction (mRSIC) method is proposed for obtaining accurate core-excitation energies in time-dependent density functional theory (TDDFT) calculations. The mRSIC method is an improvement of the RSIC method (Tsuneda et al. J Comput Chem 2003, 24, 1592). It takes into account the energy contributions from 2s and higher atomic orbitals that the RSIC method neglects. Furthermore, mRSIC improves the poor description for the nuclear-electron cusp of Gaussian basis functions. The mRSIC method was combined with a long-range correction (LC) scheme, which has been proved to give accurate valence-, Rydberg-, and charge transfer (CT)-excitation energies. In so doing, it dramatically improved the accuracy of the calculated core-excitation energies and did not affect the already accurate values of valence-, Rydberg-, and CT-excitation energies produced by the LC functionals. These results mean that the combined scheme is accurate for all excitation energy forms. © 2009 Wiley Periodicals, Inc. J Comput Chem 2009 [source] Structure, magnetizability, and nuclear magnetic shielding tensors of bis-heteropentalenes.JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 3 2006Abstract The geometry of the heteropentalenes formed by two phosphole units has been determined at the DFT level. The magnetic susceptibility and the nuclear magnetic shielding at the nuclei of these systems have also been calculated using gauge-including atomic orbitals and a large Gaussian basis set to achieve near Hartree,Fock estimates. A comparative study of the various isomers, of their flattened analogs, and of the parent phosphole molecule, shows that the [3,4-c] isomer is the most aromatic system in the set considered, assuming diatropicity and degree of planarity as indicators, even if it is the less stable in terms of total molecular energy. Plots of magnetic field-induced current densities confirm diatropicity of P-containing bis-heteropentalenenes, showing, however, significant differences from the analogous systems with distinct heteroatoms. The maps give evidence of spiral flow nearby CC bonds, compatible with prevalent distortive behavior of , electrons exalted by pyramidalization at P, and competing against the , electron compression, which would favor planar structure. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 344,351, 2006 [source] A combined freeze-and-cut strategy for the description of large molecular systems using a localized orbitals approachJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 10 2005Stefano Borini Abstract A technique to reduce the computational effort in calculating ab initio energies using a localized orbitals approach is presented. By exploiting freeze strategy at the self-consistent field (SCF) level and a cut of the unneeded atomic orbitals, it is possible to perform a localized complete active space (CAS-SCF) calculation on a reduced system. This will open the possibility to perform ab initio treatments on very large molecular systems, provided that the chemically important phenomena happen in a localized zone of the molecule. Two test cases are discussed, to illustrate the performance of the method: the cis,trans interconversion curves for the (7Z)-13 ammoniotridec-7-enoate, which demonstrates the ability of the method to reproduce the interactions between charged groups; and the cisoid,transoid energy barrier for the aldehydic group in the C13 polyenal molecule. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1042,1051, 2005 [source] Characterization of molecular orbitals by counting nodal regionsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 4 2005Yasuyo Hatano Abstract The number of nodal regions can be used as an index for characterizing molecular orbitals. A computer program has been developed to count the number of nodal regions, based on the labeling and contraction algorithms. This program is applied to the water molecule, the hydrogen sulfide molecule, the hydrogen atomic orbitals, the Rydberg excited states of ethylene, dissociation of carbon monoxide, and CASSCF calculations of formaldehyde. Because the number of nodal regions is independent of the coordinate system, the method is applicable even when the molecular structure changes drastically as in bond rotation or bond elongation. Changes of nodal regions with bond elongation are investigated for carbon monoxide. A prescription for problems arising with basis set expansion techniques is also given. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 325,333, 2005 [source] Students' levels of explanations, models, and misconceptions in basic quantum chemistry: A phenomenographic studyJOURNAL OF RESEARCH IN SCIENCE TEACHING, Issue 5 2009Christina Stefani We investigated students' knowledge constructions of basic quantum chemistry concepts, namely atomic orbitals, the Schrödinger equation, molecular orbitals, hybridization, and chemical bonding. Ausubel's theory of meaningful learning provided the theoretical framework and phenomenography the method of analysis. The semi-structured interview with 19 second-year chemistry students supplied the data. We identified four levels of explanations in the students' answers. In addition, the scientific knowledge claims reflected three main levels of models. By combining levels of explanations with levels of models, we derived four categories. Two of the categories are shades of variation in the rote-learning part of a continuum, while the other two categories are in the meaningful-learning part. All students possessed alternative conceptions some of which occurred within certain categories, while others spanned more categories. The insistence on the deterministic models of the atom, the misinterpretation of models, and the poor understanding of the current quantum concepts are main problems in the learning of the basic quantum chemistry concepts. © 2009 Wiley Periodicals, Inc. J Res Sci Teach 46: 520,536, 2009 [source] Theoretical investigation on multinuclear NMR chemical shifts of some tris(trifluoromethyl)boron complexesMAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2009Jun Zhang Abstract Tris(trifluoromethyl)boron complexes have unusual properties and may find applications in many fields of chemistry, biology, and physics. To gain insight into their NMR properties, the isotropic 11B, 13C, and 19F NMR chemical shifts of a series of tris(trifluoromethyl)boron complexes were systematically studied using the gauge-included atomic orbitals (GIAO) method at the levels of B3LYP/6-31 + G(d,p)//B3LYP/6-31G* and B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p). Solvent effects were taken into account by polarizable continuum models (PCM). The calculated results were compared with the experimental values. The reason that the structurally inequivalent fluorine atoms in a specific species give a same chemical shift in experimental measurements is attributed to the fast rotation of CF3 group around the BC(F3) bond because of the low energy barrier. The calculated 11B, 13C(F3), and 19F chemical shifts are in good agreement with the experimental measurements, while the deviations of calculated 13C(X, X = O, N) chemical shifts are slightly large. For the latter, the average absolute deviations of the results from B3LYP/6-311 + G(d,p)//B3LYP/6-311 + G(d,p) are smaller than those from B3LYP/6-31 + G(d,p)//B3LYP/6-31G*, and the inclusion of PCM reduces the deviation values. The calculated 19F and 11B chemical shieldings of (CF3)3BCO are greatly dependent on the optimized structures, while the influence of structural parameters on the calculated 13C chemical shieldings is minor. Copyright © 2009 John Wiley & Sons, Ltd. [source] DFT-GIAO 1H and 13C NMR prediction of chemical shifts for the configurational assignment of 6,-hydroxyhyoscyamine diastereoisomersMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2009Marcelo A. Muñoz Abstract 1H and 13C NMR chemical shift calculations using the density functional theory,gauge including/invariant atomic orbitals (DFT,GIAO) approximation at the B3LYP/6-311G++(d,p) level of theory have been used to assign both natural diastereoisomers of 6,-hydroxyhyoscyamine. The theoretical chemical shifts of the 1H and 13C atoms in both isomers were calculated using a previously determined conformational distribution, and the theoretical and experimental values were cross-compared. For protons, the obtained average absolute differences and root mean square (rms) errors for each comparison showed that the experimental chemical shifts of dextrorotatory and levorotatory 6,-hydroxyhyoscyamines correlated well with the theoretical values calculated for the (3R,6R,2,S) and (3S,6S,2,S) configurations, respectively, whereas for 13C atoms the calculations were unable to differentiate between isomers. The nature of the relatively large chemical shift differences observed in nuclei that share similar chemical environments between isomers was asserted from the same calculations. It is shown that the anisotropic effect of the phenyl group in the tropic ester moiety, positioned under the tropane ring, has a larger shielding effect over one ring side than over the other one. Copyright © 2009 John Wiley & Sons, Ltd. [source] NMR spectra, GIAO and charge density calculations of five-membered aromatic heterocyclesMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2007Alan R. Katritzky Abstract The B3LYP/6-31 + G(d) molecular geometry optimized structures of 17 five-membered heterocycles were employed together with the gauge including atomic orbitals (GIAO) density functional theory (DFT) method at the B3LYP/6-31 + G(d,p), B3LYP/6-311 + + G(d,p) and B3LYP/6-311 + G(2d,p) levels of theory for the calculation of proton and carbon chemicals shifts and coupling constants. The method of geometry optimization for pyrrole (1), N -methylpyrrole (2) and thiophene (7) using the larger 6-311 + + G(d,p) basis sets at the B3LYP/6-31 + G(d,p), B3LYP/6-311 + + G(d,p), B3LYP/6-31 + G(2d,p) and B3LYP/cc-pVTZ levels of theory gave little difference between calculated and experimental values of coupling constants. In general, the 1H and 13C chemical shifts for all compounds are in good agreement with theoretical calculations using the smaller 6-31 basis set. The values of nJHH(n = 3, 4, 5) and rmnJCH(n = 1, 2, 3, 4) were predicted well using the larger 6-31 + G(d,p) and 6-311 + + G(d,p) basis sets and at the B3LYP/6-31 + G(d,p), B3LYP/6-311 + + G(d,p), B3LYP/6-31 + G(2d,2p) levels of theory. The computed atomic charges [Mülliken; Natural Bond Orbital Analysis (NBO); Merz-Kollman (MK); CHELP and CHELPG] for the B3LYP/6-311 + + G(d,p) geometry optimized structures of 1,17 were used to explore correlations with the experimental proton and carbon chemical shifts. Copyright © 2007 John Wiley & Sons, Ltd. [source] Density-functional computation of 53Cr NMR chemical shiftsMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2006Michael Bühl Abstract 53Cr chemical shifts of CrO42,, Cr2O72,, CrO3X,, CrO2X2(X = F, Cl), and Cr(CO)5L (L = CO, PF3, CHNH2, CMeNMe2) are computed, using geometries optimized with the gradient-corrected BP86 density functional, at the gauge-including atomic orbitals (GIAO)-, BPW91-, and B3LYP levels. For this set of compounds, substituent effects on ,(53Cr) are better described with the pure BPW91 functional than with B3LYP, in contrast to most other transition-metal chemical shifts studied so far. For selected cases, 53Cr NMR line widths can be rationalized in terms of electric field gradients (EFGs) computed with the BPW91 functional, but in general other factors such as molecular correlation times appear to be dominating. 53Cr chemical shifts and EFGs are predicted for CrO3, Cr(C6H6)2, Cr(C6H6)CO3, and, with reduced reliability, for Cr2(µ2 -O2CH)4. Copyright © 2006 John Wiley & Sons, Ltd. [source] Compton profile study of tinPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 3 2006B. L. Ahuja Abstract In this paper we report the Compton profile of ,-tin, measured at an intermediate resolution, using 661.65-keV ,-radiation from a 137Cs source. We have also computed the Compton profiles for ,- and ,-tin using the CRYSTAL03 code. The Compton profiles within the framework of linear combination of atomic orbitals (LCAO) using Hartree,Fock (HF), density functional (DF) and pseudopotential-HF schemes embodied in the CRYSTAL03 code have been reported for both phases. Good accordance of the experiment for ,-tin with the corresponding theoretical profiles has been observed for the LCAO-HF and DF schemes. A real-space analysis of the experimental Compton profile shows the metal-like behavior of ,-tin. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Optical properties and structural phase transitions of lead-halide based inorganic,organic 3D and 2D perovskite semiconductors under high pressurePHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 14 2004K. Matsuishi Abstract Optical absorption, photoluminescence and Raman scattering of lead-halide based inorganic,organic perovskite semiconductors were measured under quasi-hydrostatic pressure at room temperature. For the 3D perovskite semiconductor, (CH3NH3)PbBr3, the free exciton photoluminescence band exhibits red-shifts with pressure, and jumps to a higher energy by 0.07 eV at 0.8 GPa, which is associated with a phase transition from a cubic to an orthorhombic structure confirmed by Raman scattering. Above the phase transition pressure, the exciton band shows blue-shifts with further increasing pressure, and eventually disappears above 4.7 GPa. The results are compared with those for the 2D perovskite semiconductor, (C4H9NH3)2PbI4. First principles pseudopotential calculations were performed to investigate changes in octahedral distortion and electronic band structures with pressure. The calculations have explained the origins of the intriguing changes in the electronic states with pressure in view of bonding characters between atomic orbitals in octahedra. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] First principles simulations of F centers in cubic SrTiO3PHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 1 2005J. Carrasco Abstract Atomic and electronic structure of regular and O-deficient SrTiO3 have been studied. Several types of first principles atomistic simulations: Hartree-Fock method, Density Functional Theory, and hybrid HF-DFT functionals, have been applied to periodic models that consider supercells of different sizes (ranging between 40 and 240 atoms). We confirm the ionic character of the Sr-O bonds and the high covalency of the Ti-O2 substructure. For the stoichiometric cubic crystal; the lattice constant and bulk modulus correctly reproduce the experimental data whereas the band gap is only properly obtained by the B3PW functional. The relaxed geometry around the F center shows a large expansion of the two nearest Ti ions. Moreover, the vacancy formation energy is extremely sensitive to the size and the shape of the supercell as well as the calculation method. The electronic density map indicates the redistribution of two electrons of the missing O atom between the vacancy and 3d atomic orbitals of the two nearest Ti ions, in contrast to the F centers in ionic oxides where the charge centroid does not change. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] X-ray atomic orbital analysis.ACTA CRYSTALLOGRAPHICA SECTION A, Issue 4 2008The scattering unit of X-ray crystal structure analysis is changed from atoms to the subshell electrons by X-ray atomic orbital analysis (XAO). All the atoms in the unit cell are divided into groups of subshell electrons in the XAO analysis. Each subshell is treated as an independent pseudo-atom, which enables the atomic orbitals (AO's) and the electron population of each AO expressed as a linear combination of s/p/d/f orbitals in each subshell to be determined. When the environmental condition of the sample is varied, the electron transfer among the AO's in the crystal can be traced with XAO. It is applicable mainly to analyses of the electron-density distribution in ionic solids including those with a nonstoichiometric structure. The expansion coefficients of each AO are calculated with the perturbation theory putting a point charge on each atom in the unit cell. This automatically makes the perturbation potential have the point-group symmetry of the atom in the crystal field. Then the coefficients of each AO are refined to fit to the observed structure factors keeping the orthonormal relationships among the AO's. Complex basis functions with , or , spin as well as real ones are employed for heavy atoms and the relationships among the coefficients for the AO's of an electron in the crystal fields of the 32 point-group symmetries are derived for p, d and f orbitals. The AO's thus derived can be applicable to an anti-symmetrized multi-electron system, although X-ray diffraction cannot specify the atomic terms occupied when the crystal symmetry permits the atom to have many terms. [source] Electronic structure calculations for inhomogeneous systems: Interfaces, surfaces, and nanocontactsANNALEN DER PHYSIK, Issue 8 2008U. Schwingenschlögl Abstract The article gives an introduction into the application of density functional theory (DFT) to inhomogeneous systems. To begin with, we describe the interplay of specific materials at interfaces, resulting in structure relaxation and modifications of the chemical bonding. We address interfaces between YBa2Cu3O7 and a normal metal, in order to quantify the intrinsic interface charge transfer into the superconductor. Moreover, we study the internal interfaces in a V6O13 battery cathode and the effects of ion incorporation during the charging and discharging process. The second part of the article deals with the influence of surfaces on the nearby electronic states. Here, we investigate a LaAlO3/SrTiO3 heterostructure in a thin film geometry. We particularly explain the experimental dependence of the electronic states at the heterointerface on the surface layer thickness. Afterwards, surface relaxations are studied for both the clean Ge(001) surface and for self-assembled Pt nanowires on Ge(001). In the third part, we turn to atomic and molecular contacts. We compare the properties of prototypical Al nanocontact geometries, aiming at insight into the chemical bonding and the occupation of the atomic orbitals. Finally, the local electronic structure of a benzene-1,4-dithiol molecule between two Au electrodes is discussed as an example for a molecular bridge. [source] Ab initio prediction of optical rotation: Comparison of density functional theory and Hartree-Fock methods for three 2,7,8-trioxabicyclo[3.2.1]octanesCHIRALITY, Issue 4 2002P.J. Stephens Abstract We report ab initio calculations of the frequency-dependent electric dipole-magnetic dipole polarizabilities, ,(,), at the sodium D line frequency and, thence, of the specific rotations, [,]D, of 2,7,8-trioxabicyclo[3.2.1]octane, 1, and its 1-methyl derivative, 2, using the Density Functional Theory (DFT) and Hartree-Fock/Self-Consistent Field (HF/SCF) methodologies. Gauge-invariant (including) atomic orbitals (GIAOs) are used to ensure origin-independent [,]D values. Using large basis sets which include diffuse functions DFT [,]D values are in good agreement with experimental values (175.8° and 139.2° for (1S,5R)- 1 and - 2, respectively); errors are in the range 25,35°. HF/SCF [,]D values, in contrast, are much less accurate; errors are in the range 75,95°. The use of small basis sets which do not include diffuse functions substantially lowers the accuracy of predicted [,]D values, as does the use of the static limit approximation: ,(,) , ,(o). The use of magnetic-field-independent atomic orbitals, FIAOs, instead of GIAOs, leads to origin-dependent, and therefore nonphysical, [,]D values. We also report DFT calculations of [,]D for the 1-phenyl derivative of 1, 3. DFT calculations find two stable conformations, differing in the orientation of the phenyl group, of very similar energy, and separated by low barriers. Values of [,]D predicted using two different algorithms for averaging over phenyl group orientations are in good agreement with experiment. In principle, the absolute configuration (AC) of a chiral molecule can be assigned by comparison of the optical rotation predicted ab initio to the experimental value. Our results demonstrate the critical importance of the choice of ab initio methodology in obtaining reliable optical rotations and, hence, ACs, and show that, at the present time, DFT constitutes the method of choice. Chirality 14:288,296, 2002. © 2002 Wiley-Liss, Inc. [source] | ||||||||||||||||