Evaluation of reaction thermochemistry using DFT calculated molecular properties: application to trans-HONO (X¹A') à HO(X²P) + NO(X²P)

Journal of the Brazilian Chemical Society

Glauco F. Bauerfeldt¹  Graciela Arbilla¹  Edilson C. Da Silva¹ 

[1] ,Universidade Federal do Rio de Janeiro Instituto de Química Rio de Janeiro RJ ,Brazil

关键词: nitrous acid;    thermochemical properties;    density functional theory;    equilibrium constants;   

DOI  :  10.1590/S0103-50532005000200010

来源: SciELO

【 摘 要 】

B3LYP calculations using basis sets up to 6-311G(3d2f,3p2d) have been employed to predict accurate thermochemical properties related to the bond dissociation reaction trans-HONO(X¹A') -> HO(X²P) + NO(X² P). A systematic study of the influence of the basis set was performed and results were compared with experimental data and with other calculated results, obtained using standard Gaussian methods (G2 and G2MP2), complete basis set extrapolation methods (CBS) and ab initio calculations (CCSD(T) and QCISD). The results suggest that, for this kind of unimolecular process: B3LYP calculations produce bond dissociation enthalpies that are more accurate than standard ab initio methods and) the best agreement with the experimental enthalpy has been found with B3LYP/6-311G(3d2f,3p2d) calculations: 49.2 kcal mol-1 and 49.0 kcal mol-1, respectively. Also, entropy and Gibbs free energy have been calculated and equilibrium constants have been determined as Keq(T) = 1.16 × 10(28) × exp(-48.34/RT), for the temperature range 200 - 500 K.

【 授权许可】

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