title: An ab initio correlated study of the potential energy surface for the HOBr.H2O complex.
abstract: The potential energy surface (PES) for the HOBr.H(2)O complex has been investigated using second- and fourth-order Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster theory with single and doubles excitations (CCSD), and a perturbative approximation of triple excitations (CCSD-T), correlated ab initio levels of theory employing basis sets of triple zeta quality with polarization and diffuse functions up to the 6-311++G(3dp,3df ) standard Pople's basis set. Six stationary points being three minima, two first-order transition state (TS) structures and one second-order TS were located on the PES. The global minimum syn and the anti equilibrium structure are virtually degenerated [DeltaE(ele-nuc) approximately 0.3 kcal mol(-1), CCSD-T/6-311++G(3df,3pd) value], with the third minima being approximately 4 kcal mol(-1) away. IRC analysis was performed to confirm the correct connectivity of the two first-order TS structures. The CCSD-T/6-311++G(3df,3pd)//MP2/6-311G(d,p) barrier for the syn<-->anti interconversion is 0.3 kcal mol(-1), indicating that a mixture of the syn and anti forms of the HOBr.H(2)O complex is likely to exist.
authors.affiliation: Laboratório de Química Inorgânica Computacional, Departamento de Química Inorgânica, Instituto de Química, Universidade Federal do Rio de Janeiro (UFRJ), Caixa Postal 68563, Rio de Janeiro, RJ, 21.945-970, Brazil.
authors.forename: Cristina Maria P
authors.initials: CM
authors.lastname: Santos
authors.forename: Roberto
authors.initials: R
authors.lastname: Faria
authors.forename: Sérgio P
authors.initials: SP
authors.lastname: Machado
authors.forename: Wagner B
authors.initials: WB
authors.lastname: De Almeida