O método DFTB, bem como a sua extensão com carga corrigida auto-consistente SCC-DFTB, tem ampliado a faixa de aplicações das ferramentas teóricas com fundamentos bem estabelecidos. Como uma aproximação do método do funcional de densidade, o método DFTB mantém aproximadamente a mesma precisão, mas com custo computacional menor, permitindo a investigação da estrutura eletrônica de sistemas grandes que não podem ser explorados com métodos ab initio convencionais. No presente artigo, os fundamentos dos métodos DFTB, SCC-DFTB e da inclusão das forças de dispersão de London são revisados. Para mostrar um exemplo da aplicabilidade do método DFTB, o equilíbrio zwitteriônico de glicina em solução aquosa é investigado. Foram realizadas simulações de dinâmica molecular usando o hamiltoniano SCC-DFTB corrigido para incluir a dispersão e uma caixa periódica contendo 129 moléculas de água, a partir de uma abordagem puramente mecânico-quântica.The DFTB method, as well as its self-consistent charge corrected variant SCC-DFTB, has widened the range of applications of fundamentally well established theoretical tools. As an approximate density-functional method, DFTB holds nearly the same accuracy, but at much lower computational costs, allowing investigation of the electronic structure of large systems which can not be exploited with conventional ab initio methods. In the present paper the fundaments of DFTB and SCC-DFTB and inclusion of London dispersion forces are reviewed. In order to show an example of the DFTB applicability, the zwitterionic equilibrium of glycine in aqueous solution is investigated by molecular-dynamics simulation using a dispersion-corrected SCC-DFTB Hamiltonian and a periodic box containing 129 water molecules, in a purely quantum-mechanical approach.

A systematic study of neutral and charged 3d-metal trioxides and tetraoxides Toward accurate thermochemical models for transition metals: G3Large basis sets for atoms Sc-Zn Electronic structure and chemical bonding between the first row transition metals and C 2 : A photoelectron spectroscopy study of MC 2 − (M=Sc, V, Cr, Mn, Fe, and Co)

Energy gaps have been estimated for -OMe and -NO 2 R,R′-substituted oligothiophenes up to six monomers using semiempirical, Hartree-Fock and density functional methods. Scaled values calculated using noncorrelated methods are in good agreement with the experimental values, and so were nonscaled estimates predicted by density functional methods. Error bars are ca. 0.2 eV for all 11 oligothiophenes studied. The influence of the quality of the basis set on the energy estimates is discussed. The discrepancy observed for the -OMeand -NO 2 -substituted sexithiophene result with respect to the experimental value is discussed and has been attributed to a charge transfer in the molecule. The ∆SCF approach has been found to be an alternative way to estimate energy gaps for molecular systems where Koopmans' theorem may not provide good results. Implications for predictions of HOMO-LUMO gaps of π-conjugated systems are discussed and analyzed in terms of designing new materials with controlled properties.

The potential energy surface (PES) for the 2,2′-bithiophene molecule was investigated using Hartree–Fock, correlated MP2, MP4(SDQ), CCSD, and density functional theory levels. Distinct basis sets ranging from double-zeta to triple-zeta quality, with polarization functions added on all atoms, were employed as well as the Dunning correlated consistent polarized valence double-zeta (cc-pVDZ) basis set. Single point configuration interaction CISD calculations were also performed using the cc-pVDZ basis set. Harmonic frequency calculations were performed for the unambiguous characterization of the stationary points located on the PES and also to calculate thermal Gibbs free energy corrections. Regarding the structural predictions we found that the B3LYP/6-311G** and MP2/cc-pVDZ fully optimized geometries exhibit the best agreement with the gas phase electron diffraction data. The calculated B3LYP/6-311G**, MP2/cc-pVDZ and experimental torsional angle for the syn-gauche structure are, respectively, 37.4° (B3LYP), 39.9° (MP2), and 36°±5° (expt.) with the corresponding values for the anti-gauche form being, respectively, 150.3° (B3LYP), 146.0° (MP2), and 148°±3° (expt.). The relative energy between the two minima and torsional barriers are sensitive both to the size of the basis set and the level of the quantum mechanical method used. Therefore, larger basis sets are needed to assess the ability of the DFT approach for describing torsional barriers. The MP4(SDQ) and CCSD relative energy results, reported in this work, can be considered as the most reliable torsional potential data available for the 2,2′-bithiophene molecule. Our results indicate that the experimentally estimated relative energy value for the two equilibrium structures present on the PES for the bithiophene molecule, and consequently the relative abundance of the anti-gauche species, is somewhat underestimated. By comparison with MP4(SDQ) and CCSD results we have shown that single point DFT/6-311G** calculations using HF/6-31G* geometries is the most computationally efficient procedure to study bithiophene like systems, with energy barriers agreeing within 2 kJ/mol.

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