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Internal‐rotation and inversion potential energy surfaces for methylamine and methylphosphine
Author(s) -
Kim HaeWon,
Zeroka Daniel
Publication year - 2007
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21564
Subject(s) - methylamine , inversion (geology) , internal rotation , chemistry , internal energy , basis set , transition state , potential energy surface , atomic physics , rotation (mathematics) , potential energy , quantum , computational chemistry , molecular physics , physics , molecule , thermodynamics , quantum mechanics , mathematics , geometry , density functional theory , geology , mechanical engineering , paleontology , organic chemistry , structural basin , engineering , catalysis , biochemistry
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. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008