Simulation of the infrared predissociation spectra of H-5(+)

作者：Aguado Alfredo; Sanz Sanz Cristina; Villarreal Pablo; Roncero Octavio^*

来源：Physical Review A, 2012, 85(3): 032514.

DOI：10.1103/PhysRevA.85.032514

A quantum study of the bound states and infrared predissociation spectra of H-5(+) is done using a recently proposed global and accurate potential-energy surface [Aguado et al., J. Chem. Phys. 133, 024306 (2010)]. The bound states are calculated for seven degrees of freedom using an iterative Lanczos method, yielding a dissociation energy in very good agreement with the available experimental data. The predissociation states are described by a wave-packet treatment considering a shared-proton model, in which the three-dimensional motion of the central atom is described using non-Jacobi bond coordinates. The justification of this model is that the change in the electric dipole moment is larger as a function of the motion of the central atom, responsible for the proton transfer in the H-3(+) + H-2 -%26gt; H-2 + H-3(+) reaction. The electric dipole moment is calculated at the level of coupled-cluster theory with single and double excitations and fitted in nine dimensions to an analytical function. With it, the infrared predissociation spectrum is simulated, yielding a reasonable agreement with recent measurements.

• 出版日期2012-3-16