Using the HF, MP2, and DFT methods with a 6-311G** basis set, we examine the internal-rotation and inversion of the amino and phosphino groups in methylamine and methylphosphine. The resulting energy surfaces are reported as a function of rotation and inversion descriptors. Both surfaces are characterized by several special points: three minimum energy states, three first-order internal-rotation transition states, six first-order inversion transition states, and six second-order inversion transition states. The MP2 method gave better agreement with experiment. For methylamine, the MP2 energy barrier for internal-rotation is 8.73 kJ/mol; for first-order inversion it is 22.80 kJ/mol and for second-order inversion it is 22.41 kJ/mol. For methylphosphine, the MP2 energy barriers are 7.53, 149.88, and 149.65 kJ/mol, respectively. The energy barriers include ZPE correction contributions.
All Science Journal Classification (ASJC) codes
- Atomic and Molecular Physics, and Optics
- Condensed Matter Physics
- Physical and Theoretical Chemistry