title: Molecular properties of the PCO radical: heat of formation and the isomerization pathways.
abstract: The potential energy surface of [P,C,O] system in the ground state was investigated by quantum chemical methods. Four different isomers were characterized at the B3LYP/aug-cc-pVTZ: COP (i1), cPCO (i2), PCO (i3), and CPO (i4). The linear species i3 is the global minimum in the ground state surface, while i4 is a bent structure, and i2 is a cyclic isomer. In view to evaluate the bond nature of each isomer, a QTAIM and a NBO analyses were applied. The triangular species presents a ring critical point which confirms its cyclic structure instead of a T-shape one. The stability increases in the following order: i3 > i2 > i1 > i4. The energy gap between i3 and i2 ranges from 49.20 to 51.15 kcal mol(-1). The reaction barrier energies that converge into the direction of i3 showed values around 10 kcal mol(-1), while the reverse barriers are considerably large (62.85 kcal mol(-1)). The i3 heat of formation at 298 K ranges from 11.83 to 19.41 kcal mol(-1).
authors: Instituto de Química de São Carlos, Universidade de São Paulo, USP, São Carlos, SP, Brasil, rommelbv@yahoo.com.br.
authors: Rommel B
authors: RB
authors: Viana
authors: Amanda R
authors: AR
authors: Guimarães
authors: Aguinaldo R
authors: AR
authors: de Souza
authors: Albérico B F
authors: AB
authors: da Silva
mesh_terms: D004734:Energy Metabolism; D007536:Isomerism; D007700:Kinetics; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics