Theoretical study on the methane activation reactions by Pt, Pt+, and Pt- atoms

M. Hada, H. Nakatsuji, Hiromi Nakai, S. Gyobu, S. Miki

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The oxidative additions of CH4 to the ground and excited states of Pt, Pt-, and Pt+ species are studied by the symmetry-adapted cluster (SAC) and SAC-CI methods. The reaction path is examined by calculating the Hellmann-Feynman forces acting on C and H atoms of CH4. It involves the transition state and/or the activated complex. The activation energies of CH4 with the triplet Pt(3D; 5d9s1), singlet Pt(1 S; 5d10), anion Pt-(2S; 5d106s1), Pt-(2P; 5d106p1), and cation Pt+(2D; 5d9) are 102, 59, 75, 41, and 52 kcal mol- respectively. Further, there is a possibility for the excited state of the Pt- + CH4 system that the reaction proceeds with lower activation energy by relaxing onto the ground state curve along the reaction process. The activated complex Pt-(H)(CH3) is 29 kcal mol- more stable than the dissociation limit of the excited Pt- + CH4 system. This suggests the possibility of C-H activation by photoexcited Pt-. In the Pt- (H)(CH3) complex, both bent and linear forms are possible; the two forms transform through an energy barrier of 22 kcal mol-1. In the Pt and Pt+ complexes, only the bent forms are stable.

Original languageEnglish
Pages (from-to)207-212
Number of pages6
JournalJournal of Molecular Structure: THEOCHEM
Volume281
Issue number2-3
DOIs
Publication statusPublished - 1993 Apr 30
Externally publishedYes

Fingerprint

Methane
Excited states
Ground state
Anions
Cations
Theoretical Models
methane
Activation energy
Chemical activation
activation
Atoms
Energy barriers
activation energy
atoms
Negative ions
ground state
Positive ions
symmetry
excitation
dissociation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Theoretical study on the methane activation reactions by Pt, Pt+, and Pt- atoms. / Hada, M.; Nakatsuji, H.; Nakai, Hiromi; Gyobu, S.; Miki, S.

In: Journal of Molecular Structure: THEOCHEM, Vol. 281, No. 2-3, 30.04.1993, p. 207-212.

Research output: Contribution to journalArticle

Hada, M. ; Nakatsuji, H. ; Nakai, Hiromi ; Gyobu, S. ; Miki, S. / Theoretical study on the methane activation reactions by Pt, Pt+, and Pt- atoms. In: Journal of Molecular Structure: THEOCHEM. 1993 ; Vol. 281, No. 2-3. pp. 207-212.
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