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The PH 2 +PH 2 multichannel reaction path was proposed in this study. The transition state that connects the reactants to cis-P 2 H 2 isomer was found for the first time ever. This process is not allowed to occur at ordinary conditions because of its high energy barrier, 70kcalmol −1 . The PH 2 +PH 2 disproportionation to form the triplet PH 3 radical is an exothermic and spontaneous reaction. The PH 2 +PH 2 reaction may also form the P 2 H 4 molecule in the absence of surfaces.
Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São Carlense, 400 C.P. 780 São Carlos, SP 13566-590, Brazil
Departamento de Química, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente 225, Gávea, 22453-900 Rio de Janeiro, RJ, Brazil