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Theoretical prediction regarding structural and thermodynamical characteristics of stable CH 3 PO 2 isomers and unimolecular decomposition mechanisms of species CH 3 P(O) 2 , CH 3 OPO, and CH 2 P(O)OH
Author(s) -
Kan Wei,
Zhong Hua,
Yu HaiTao
Publication year - 2009
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21241
Subject(s) - isomerization , chemistry , dissociation (chemistry) , potential energy surface , adiabatic process , bond dissociation energy , transition state , computational chemistry , decomposition , molecule , potential energy , transition state theory , thermodynamics , reaction rate constant , kinetics , atomic physics , organic chemistry , physics , quantum mechanics , catalysis
The detailed isomerization and dissociation reaction potential energy profile of the CH 3 PO 2 system was established at the UCCSD(T)/6‐311++G(3df,2p)//UB3LYP/6‐311++G(d,p) level of theory. Seventy minimum isomers were located and connected by 93 optimized interconversion transition states. Furthermore, 32 isomers with high kinetic stability were predicted to be possible candidates for further experimental detection. The bonding nature of the suggested stable isomers was analyzed while their molecular properties including heats of formation, adiabatic ionization potentials, and adiabatic electronic affinities were calculated at the G2, G2(MP2), G3, and CBS‐Q levels. Based on the isomerization and dissociation potential energy surface, possible unimolecular decomposition mechanisms and pathways of the low‐lying molecules CH 3 P(O) 2 , CH 3 OPO, and CH 2 P(O)OH were discussed. Furthermore, the transition state theory rate constants of the primary unimolecular dissociation channels were also calculated. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009