Internal-rotation and inversion potential energy surfaces for methylamine and methylphosphine

Hae-Won Kim, Daniel Zeroka

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

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.

Original languageEnglish (US)
Pages (from-to)974-982
Number of pages9
JournalInternational Journal of Quantum Chemistry
Volume108
Issue number5
DOIs
StatePublished - Apr 1 2008

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Potential energy surfaces
Energy barriers
potential energy
inversions
Electron transitions
Interfacial energy
Discrete Fourier transforms
Electron energy levels
energy
surface energy
methylamine
Experiments

All Science Journal Classification (ASJC) codes

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

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abstract = "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.",
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Internal-rotation and inversion potential energy surfaces for methylamine and methylphosphine. / Kim, Hae-Won; Zeroka, Daniel.

In: International Journal of Quantum Chemistry, Vol. 108, No. 5, 01.04.2008, p. 974-982.

Research output: Contribution to journalArticle

TY - JOUR

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AB - 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.

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