Spin-polarized Hartree-Fock-Slater calculations in atoms and diatomic molecules with the finite element method

We present spin-polarized Hartree-Fock-Slater calculations performed with the highly accurate numerical finite element method for the atoms N and 0 and the diatomic radical OH as examples.

Solution of the Hartree-Fock-Slater equations for diatomic molecules by the finite-element method

We present the finite-element method in its application to solving quantum-mechanical problems for diatomic molecules. Results for Hartree-Fock calculations of H_2 and Hartree-Fock-Slater calculations for molecules like N_2 and CO are presented. The accuracy achieved with fewer than 5000 grid points for the total energies of these systems is 10^-8 a.u., which is about two orders of magnitude better than the accuracy of any other available method.

Force constants and dipole moment derivatives of molecules from perturbed Hartree-Fock calculations II. Applications to limited basis set SCF-MO wavefunctions

The perturbed Hartree–Fock theory developed in the preceding paper is applied to LiH, BH, and HF, using limited basis‐set SCF–MO wavefunctions derived by previous workers. The calculated values for the force constant ke and the dipole‐moment derivative μ(1) are (experimental values in parentheses): LiH, ke  =  1.618(1.026)mdyn/Å,μ(1)  =  −18.77(−2.0±0.3)D/ÅBH,ke  =  5.199(3.032)mdyn/Å,μ(1)  =  −1.03(−)D/Å;HF,ke  =  12.90(9.651)mdyn/Å,μ(1)  =  −2.15(+1.50)D/Å. The values of the force on the proton were calculated exactly and according to the Hellmann–Feynman theorem in each case, and the discrepancies show that none of the wavefunctions used are close to the Hartree–Fock limit, so that the large errors in ke and μ(1) are not surprising. However no difficulties arose in the perturbed Hartree–Fock calculation, so that the application of the theory to more accurate wavefunctions appears quite feasible.

Unrestricted Skyrme-tensor time-dependent Hartree-Fock model and its application to the nuclear response from spherical to triaxial nuclei

The nuclear time-dependent Hartree-Fock model formulated in three-dimensional space, based on the full standard Skyrme energy density functional complemented with the tensor force, is presented. Full self-consistency is achieved by the model. The application to the isovector giant dipole resonance is discussed in the linear limit, ranging from spherical nuclei (16O and 120Sn) to systems displaying axial or triaxial deformation (24Mg, 28Si, 178Os, 190W and 238U). Particular attention is paid to the spin-dependent terms from the central sector of the functional, recently included together with the tensor. They turn out to be capable of producing a qualitative change on the strength distribution in this channel. The effect on the deformation properties is also discussed. The quantitative effects on the linear response are small and, overall, the giant dipole energy remains unaffected. Calculations are compared to predictions from the (quasi)-particle random-phase approximation and experimental data where available, finding good agreement

Ab initio study of high tridymite by the formalism generator coordinate Hartree-Fock

The Generator Coordinate Hartree-Fock (GCHF) Method is applied to generate extended 14s 8p and 17s 11p Gaussian basis sets for the atoms O and Si, respectively. The role of the weight functions in the assessment of the numerical integration range of the GCHF is shown. The Gaussian basis sets are contracted to [6s4p] O atom and [8s5p] Si atom by the Dunning's segmented contraction scheme. To evaluate the quality of our contracted [6s4p] and [8s5p] bases in molecular calculations we accomplish calculations of total and orbital energies in the Hartree-Fock-Roothaan method for O-2 and SiO molecules. We compare the results obtained with the our (14s 8p) and (17s 11p) bases sets with the of 6-311G basis and with values from the literature. The addition of one d polarization function in the silicon basis and its utilization with the basis for oxygen leads to the calculation of electronic properties and IR Spectrum of high tridymite in space group D-3d. (C) 1999 Elsevier B.V. B.V. All rights reserved.

The generator coordinate Hartree-Fock method as strategy for building Gaussian basis sets to ab initio study of the process of adsorption of sulfur on platinum (200) surface

The scheme named generator coordinate Hartree-Fock method (GCHF) is used to build (22s14p) and (33s22p16d9f) gaussian basis sets to S ((3)P) and Pt ((3)D) atoms, respectively. Theses basis sets are contracted to [13s10p] and [19s13p9d5f] through of Dunning's segmented contraction scheme and are enriched with d and g polarization functions, [13s10p1d] and [19s13p9d5flg]. Finally, the [19s13p9d5f1g] basis Set to Pt ((3)D) was supplemented with s and d diffuse functions, [20s13p10d5flg], and used in combination with [13s10p1d] to study the effects of adsorption of S ((3)D) atom on a pt ((3)D) atom belonged to infinite Pt (200) surface. Atom-atom overlap population, bond order, and infrared spectrum of [pt(_)S](2 -) were calculated properties and were carried out at Hartree-Fock-Roothaan level. The results indicate that the process of adsorption of S ((3)P) on pt ((3)D) in the infinite Pt (200) surface is mainly caused by a strong contribution of sigma between the 3p(z) orbital of S ((3)P) and the 6s orbital of pt ((3)D). (c) 2004 Elsevier B.V. All rights reserved.

Gaussian basis sets by generator coordinate Hartree-Fock method to ab initio calculations of electron affinities of enolates

The Generator Coordinate Hartree-Fock (GCHF) method is employed to generate uncontracted 15s and 18s11p gaussian basis sets for the H, C and O atoms, respectively. These basis sets are then contracted to 3s and 4s H atom and 6s5p, for C and O atoms by a standard procedure. For quality evaluation of contracted basis sets in molecular calculations, we have accomplished calculations of total and orbital energies in the Hartree-Fock-Roothaaii (HFR) approach for CH, C(2) and CO molecules. The results obtained with the uncontracted basis sets are compared with values obtained with the standard D95, 6-311G basis sets and with values reported in the literature. The 4s and 6s5p basis sets are enriched with polarization and diffuse functions for atoms of the parent neutral systems and of the enolates anions (cycloheptanone enolate, 2,5-dimethyleyelopentanone enolate, 4-heptanone enolate, and di-isopropyl ketone enolate) from the literature, in order to assess their performance in ab initio molecular calculations, and applied for calculations of electron affinities of the enolates. The calculations were performed at the DFT (BLYP and B3LYP) and HF levels and compared with the corresponding experimental values and with those obtained by using other 6-3 1 + +G((*)) and 6-311 + +G((*)) basis sets from literature. For the enolates studied, the differences between the electron affinities obtained with GCHF basis sets, at the B3LYP level, and the experimental values are -0.001, -0,014, -0.001, and -0.001 eV. (C) 2002 Elsevier B.V. B.V. All rights reserved.

H- 'H POT. +' e HE- 'H POT. +' confinados via método Hartree-Fock

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Investigação das características I x V e C x V de NCPS puro, com nitrogênio substitucional carregado (-1 e +1) e com grupos doador (NO2)-aceitador (NH2) através de métodos derivados de hartree-fock

Neste trabalho, fizemos uma investigação sobre o estudo teórico das características I x V e C x V de Nanotubo Carbono de Parede Simples (NCPS) puro, com Nitrogênio substitucional carregado com cargas -1 (caracterizando um indicativo de dopagem tipo n) e +1 (caracterizando um indicativo de dopagem tipo p) e na presença de grupos doador (NO₂)-aceitador (NH₂), através da simulação computacional do estado fundamental de NCPS, bem como de sua estrutura eletrônica e propriedades ópticas, utilizando parametrizações semi-empíricas AM1 (Austin Mudel 1) e ZINDO/S-ClS (Zerner´s lntermediate Neglect of Differential Orbital/Spectroscopic - Cunfiguration lnteraction Single) derivadas da Teoria de Hartree-Fock baseada em técnicas de química quântica. Por meio deste modelo teórico analisamos as propriedades ópticas e eletrônicas, de maior interesse para esses materiais, a fim de se entender a melhor forma de interação desses materiais na fabricação de dispositivos eletrônicos, tais como TECs (Transistores de Efeito de Campo) ou em aplicações em optoeletrônica tais como DEL (Dispositivo Emissor de Luz). Observamos que NCPS com Nitrogênio substitucional apresentam defeitos conformacionais do tipo polarônico. Fizemos as curvas dos espectros UV-visível de Absorção para NCPS armchair e zigzag puro, com Nitrogênio substitucional carregado com cargas (-1 e +1) e na presença de grupos doador (NO₂)-aceitador (NH₂), quando perturbados por intensidades diferentes de campo elétrico. Verificamos que em NCPS zigzag ao aumentarmos a intensidade do campo elétrico, suas curvas sofrem grandes perturbações. Obtivemos as curvas p x E, I x V e C x V para esses NCPS, concluímos que NCPS armchair possui comportamento resistor, pois suas curvas são lineares e zigzag possui comportamento semelhante ao dos dispositivos eletrônicos importantes para o avanço tecnológico. Assim, nossos resultados estão de bom acordo com os resultados experimentais e teóricos de NCPS puro e com Nitrogênio encontrados na literatura.

The generator coordinate method in the unrestricted Hartree-Fock formalism

The generator coordinate method was implemented in the unrestricted Hartree-Fock formalism. Weight functions were built from Gaussian generator functions for 1s, 2s, and 2p orbitals of carbon and oxygen atoms. These weight functions show a similar behavior to those found in the generator coordinate restricted Hartree-Fock method, i.e., they are smooth, continuous, and tend to zero in the limits of integration. Moreover, the weight functions obtained are different for spin-up and spin-down electrons what is a result from spin polarization. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

Il metodo di Hartree-Fock

Il metodo Hartree-Fock permette di determinare approssimativamente la funzione d'onda e l'energia per atomi a più elettroni in uno stato stazionario. Più in generale, si applica a sistemi quantistici a N-corpi, per studiare, ad esempio, gli elettroni nelle molecole e nei solidi. Il punto di partenza di questo metodo è il modello della particella indipendente; sotto questa ipotesi, ogni elettrone del sistema è descritto dalla propria funzione d'onda. Il contributo di D. R. Hartree allo studio della struttura di atomi complessi consiste nell'aver formulato le equazioni per le funzioni d'onda dei singoli elettroni usando argomentazioni intuitive e nell'avere inoltre proposto, per la loro risoluzione, una procedura iterativa basata sul requisito di autoconsistenza. La generalizzazione del suo metodo, che tiene conto del requisito di antisimmetria imposto dal principio di esclusione di Pauli, fu formulata da V. A. Fock e J. C. Slater. Con tale tecnica si assume che la funzione d'onda totale a N-elettroni sia un determinante di Slater, ovvero un prodotto antisimmetrico di orbitali relativi a singoli elettroni. Il determinante di Slater ottimale si ottiene usando il metodo variazionale per individuare i migliori spin-orbitali.

The Hartree-Fock Method Applied to Helium's Electrons

The difficulties of applying the Hartree-Fock method to many body problems is illustrated by treating Helium's electrons up to the point where tractability vanishes. Second, the problem of applying Hartree-Fock methods to the helium atom's electrons, when they are constrained to remain on a sphere, is revisited. The 6-dimensional total energy operator is reduced to a 2-dimensional one, and the application of that 2-dimensional operator in the Hartree-Fock mode is discussed.