Computational Studies of Gas-Phase Ca3P2 and Ca6P4

The electronic and molecular structures of Ca3P2 and Ca6P4 are investigated using high-level ab initio methods. The lowest energy structure for Ca3P2 is found to be a Jahn−Teller distorted triplet. An excited-state singlet is found with various post HF methods; however, DFT incorrectly predicts a cl...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2009-09, Vol.113 (35), p.9737-9740
Main Authors: Gamage, Chammi S. Palehepitiya, Ueno-Noto, Kaori, Marynick, Dennis S
Format: Article
Language:English
Subjects:
A: Molecular Structure, Quantum Chemistry, General Theory
Online Access:Get full text
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Summary:The electronic and molecular structures of Ca3P2 and Ca6P4 are investigated using high-level ab initio methods. The lowest energy structure for Ca3P2 is found to be a Jahn−Teller distorted triplet. An excited-state singlet is found with various post HF methods; however, DFT incorrectly predicts a closed shell singlet to be the ground state. For the Ca6P4 system, both DFT and ab initio methods give consistent relative energies. The computational results demonstrate that the energetics are very sensitive to the size of the Ca basis set. Enhancing the Ca basis sets with additional s and p valence functions significantly affects the calculated energies.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp9050935