Energetics of C-N coupling reactions on Pt(111) and Ni(111) surfaces from application of density-functional theory

Wei Jia Chen, Chen Hao Yeh, Chun Chih Chang, Jia-Jen Ho

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Abstract

We applied density-functional theory (DFT) with the projector-augmented- wave method (PAW) to investigate systematically the energetics of C-N coupling reactions on Pt(111) and Ni(111)surfaces. Our approach includes several steps: the adsorption of reactants and products (CHx, NHy and CHxNHy, x = 0-3, y = 0-2), movement of molecular fragments on the surface, and then C-N coupling. According to our calculations, the energies (ignoring the conventional negative sign) of adsorption of CH x and NHy on Pt(111)/Ni(111) surfaces decrease in the order C > CH > CH2 > CH3 and N > NH > NH2, with values 7.41/6.91, 6.97/6.52, 4.58/4.39, 2.19/2.01 eV and 5.10/5.49, 4.12/4.79, 2.75/2.87 eV, respectively. Regarding the adsorption energies among CHxNHy, the adsorption energy of CNH 2 species is the highest on the Pt(111) surface, whereas on the Ni(111) surface CH3N is the most stable. The C-N coupling barriers differ on the two metallic surfaces despite the structures of initial, transition and final states being similar. On the Pt(111) surface, the coupling reaction of CH2 + NH2 has the smallest barrier, whereas CH + NH2 is the most favorable on the Ni(111) surface. The detailed local density of states (LDOS) and electron-localization functions (ELF) were investigated to rationalize the calculated outcomes.

Original languageEnglish
Pages (from-to)10395-10401
Number of pages7
JournalPhysical Chemistry Chemical Physics
Volume15
Issue number25
DOIs
Publication statusPublished - 2013 Jul 7

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Adsorption
Density functional theory
density functional theory
adsorption
methylidyne
Electrons
projectors
energy
fragments
products
electrons

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Energetics of C-N coupling reactions on Pt(111) and Ni(111) surfaces from application of density-functional theory. / Chen, Wei Jia; Yeh, Chen Hao; Chang, Chun Chih; Ho, Jia-Jen.

In: Physical Chemistry Chemical Physics, Vol. 15, No. 25, 07.07.2013, p. 10395-10401.

Research output: Contribution to journalArticle

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N2 - We applied density-functional theory (DFT) with the projector-augmented- wave method (PAW) to investigate systematically the energetics of C-N coupling reactions on Pt(111) and Ni(111)surfaces. Our approach includes several steps: the adsorption of reactants and products (CHx, NHy and CHxNHy, x = 0-3, y = 0-2), movement of molecular fragments on the surface, and then C-N coupling. According to our calculations, the energies (ignoring the conventional negative sign) of adsorption of CH x and NHy on Pt(111)/Ni(111) surfaces decrease in the order C > CH > CH2 > CH3 and N > NH > NH2, with values 7.41/6.91, 6.97/6.52, 4.58/4.39, 2.19/2.01 eV and 5.10/5.49, 4.12/4.79, 2.75/2.87 eV, respectively. Regarding the adsorption energies among CHxNHy, the adsorption energy of CNH 2 species is the highest on the Pt(111) surface, whereas on the Ni(111) surface CH3N is the most stable. The C-N coupling barriers differ on the two metallic surfaces despite the structures of initial, transition and final states being similar. On the Pt(111) surface, the coupling reaction of CH2 + NH2 has the smallest barrier, whereas CH + NH2 is the most favorable on the Ni(111) surface. The detailed local density of states (LDOS) and electron-localization functions (ELF) were investigated to rationalize the calculated outcomes.

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