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Analysis of vibrational modes of the P 4 molecule through hyperspherical variants of the local orthogonal coordinates: The limit of dissociation in dimers
Author(s) -
Ragni Mirco,
Prudente Frederico V.,
Bitencourt Ana C. P.,
Barreto Patricia R. P.
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22763
Subject(s) - ground state , dissociation (chemistry) , chemistry , molecule , coupled cluster , singlet state , atomic physics , multireference configuration interaction , wave function , molecular vibration , electronic structure , molecular physics , physics , configuration interaction , computational chemistry , quantum mechanics , excited state
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 P 4 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. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010