Analysis of Vibrational Modes of the P-4 Molecule Through Hyperspherical Variants of the Local Orthogonal Coordinates: The Limit of Dissociation in Dimers

作者：Ragni Mirco^*; Prudente Frederico V; Bitencourt Ana C P; Barreto Patricia R P

来源：International Journal of Quantum Chemistry, 2011, 111(7-8): 1719-1733.

DOI：10.1002/qua.22763

• orthogonal local coordinates
• orthogonal Hamiltonian
• cluster of phosphours
• hyperspherical coordinates

In this work, we discuss the representation in different orthogonal coordinates sets of highly symmetric P-4 molecule whose equilibrium configuration is tetrahedral. For this purpose, the H (or diatom-diatom) and Wigner orthogonal representations are used to study the singlet (ground) electronic state of the title molecule, whereas the V (or diatom-satellites) scheme is used in the triplet electronic state analysis. The equilibrium geometries and the respective electronic energies of P-n, n = 1, ... , 4, are determined using the coupled cluster and DFT methodologies. Moreover, the vibrational harmonic modes and the minimum energy path of the P4 dissociation in P-2 dimers are calculated within DFT procedure. From these calculations, the diatom-diatom and Wigner vectors are used to analyze the behavior of vibrational modes, and the possible fragmentation channels (P-4 --> 2P(2), P-3 + P, P-2 + 2P, 4P) are discussed. The presented results are compared, when available, with previous theoretical and experimental ones.

• 出版日期2011-7