Importância das cooperativas de crédito para fornecedores de cana-de-açúcar: um estudo de caso

No presente trabalho analisa-se a importância das cooperativas no mercado de crédito rural do Brasil, com foco na visão de quem demanda empréstimos. Para tanto, realizou-se um estudo de caso referente à Cooperativa de Crédito Rural dos Fornecedores de Cana e Agropecuaristas da Região de Piracicaba (Cocrefocapi). O objetivo principal é mostrar a importância da Cocrefocapi no financiamento dos fornecedores de cana de Piracicaba, a partir da análise da influência de vários fatores presentes na decisão dos cooperados em escolher esta instituição como principal financiadora. Assim, foram elaborados e testados dois modelos econométricos de resposta qualitativa, além de várias análises descritivas. Os resultados mostram que o tamanho da terra é um fator que deve ser considerado ao se analisar a demanda por crédito agrícola. Além disso, não existe evidência econométrica que mostre que os associados com maior participação no capital institucional da Cocrefocapi tenham maiores incentivos para tomar empréstimos junto à cooperativa. Por outro lado, embora os fornecedores que tomaram empréstimos na Cocrefocapi a tenham escolhido principalmente por menores custos de transação, os resultados indicam que muitas destas pessoas tomaram empréstimos em outras instituições, pois, além de produzirem cana, conduzem outras atividades econômicas que não são financiadas pela Cocrefocapi.

Computation of (3)J(HH) coupling constants with a combination of density functional theory and semiempirical calculations. Application to complex molecules

This work evaluates the efficiency of economic levels of theory for the prediction of (3)J(HH) spin-spin coupling constants, to be used when robust electronic structure methods are prohibitive. To that purpose, DFT methods like mPW1PW91. B3LYP and PBEPBE were used to obtain coupling constants for a test set whose coupling constants are well known. Satisfactory results were obtained in most of cases, with the mPW1PW91/6-31G(d,p)//B3LYP/6-31G(d,p) leading the set. In a second step. B3LYP was replaced by the semiempirical methods PM6 and RM1 in the geometry optimizations. Coupling constants calculated with these latter structures were at least as good as the ones obtained by pure DFT methods. This is a promising result, because some of the main objectives of computational chemistry - low computational cost and time, allied to high performance and precision - were attained together. (C) 2012 Elsevier B.V. All rights reserved.

Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.