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Article

An Investigation of the BCP Potential Energy Surface

Hyun Joo and Michael L. McKee*

Department of Chemistry, Auburn University, Auburn, Alabama 36849

J. Phys. Chem. A, 2004, 108 (10), pp 1851–1859

DOI: 10.1021/jp031170b

Publication Date (Web): February 11, 2004

Author to whom correspondence should be addressed. E-mail: mckee@ chem.auburn.edu.

Abstract

The singlet and triplet potential energy surfaces (PESs) of boron−carbon−phosphorus (BCP) isomers were investigated, using various theoretical methods. Geometries of the minima and transition states on the PES were optimized at the B3LYP/6-311+G(2df) and CASSCF(12,12)/6-311+G(2df) levels, and single-point calculations were made at the CASPT2/ANO-L level, to consider dynamic electron correlation effects. The most-stable isomer was linear singlet BCP (¹Σ⁺); its calculated heat of formation (Δ_fH°, 0 K) is 150.5 ± 2 kcal/mol. Study of the fragmentation processes in BCP revealed that the bond enthalpies of the B−C and C−P bonds in BCP (¹Σ⁺) at 0 K are 111.7 and 128.9 kcal/mol, respectively, at the CASPT2/ANO-L level. A possible crossing mechanism between two electronic states (³A‘ and ³A‘ ‘) is discussed, and Renner−Teller species with ³Π state symmetry are investigated.

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