Reactions of hydrazoic acid and trimethylindium on TiO 2 rutile (110) surface

A computational study on the formation of the first monolayer InN

Jeng-Han Wang, M. C. Lin

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12 Citations (Scopus)

Abstract

This Article reports the result of a computational study on the reaction of hydrazoic acid and trimethylindium (TMIn), coadsorbed on TiO 2 rutile (110) surface. The adsorption geometries and energies of possible adsorbates including HN 3 -In(CH 3 ) 3 (a) and its derivatives, HN 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 )(a), and N-In(a), have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. The mechanisms of these surface reactions have also been explicitly elucidated with the computed potential energy surfaces. Starting from the interaction of three stable HN 3 adsorbates, HN 3 -O b (a), H(N 2 )N-O b (a), and Ti-NN(H)N-O b (a), where O b is the bridged O site on the surface, with two stable intermediates from the adsorption and dissociative adsorption of TMIn, (H 3 C) 3 In-O b (a) and (H 3 C) 2 In-Ob(a) + H 3 C-O b (a), InN products can be formed exothermically via four reaction paths following the initial barrierless In-atom association with the N atom directly bonded to H, by CH 4 elimination (with ∼40 kcal/mol barriers), the InN-N bond breaking and the final CH 3 elimination or migration (with <20 kcal/mol barriers). These Langmuir - Hinshelwood processes producing the two most stable InN(a) side-on adsorptions confirm that HN 3 and TMIn are indeed very efficient precursors for the deposition of InN films on TiO 2 nanoparticles. The result of similar calculations for the reactions occurring by the Rideal - Eley mechanism involving HN 3 (a) + TMIn(g) and HN 3 (g) + TMIn(a) indicates that they are energetically less favored and produce the less stable InN(a) with end-on configurations.

Original languageEnglish
Pages (from-to)2263-2270
Number of pages8
JournalJournal of Physical Chemistry B
Volume110
Issue number5
DOIs
Publication statusPublished - 2006 Feb 9

Fingerprint

hydrazoic acid
rutile
Monolayers
methylidyne
Adsorption
Acids
Adsorbates
adsorption
Atoms
Potential energy surfaces
elimination
Surface reactions
Density functional theory
Association reactions
Nanoparticles
Derivatives
surface reactions
pseudopotentials
atoms
Geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

@article{820d5c9471fa489f9bd457e59555c6cf,
title = "Reactions of hydrazoic acid and trimethylindium on TiO 2 rutile (110) surface: A computational study on the formation of the first monolayer InN",
abstract = "This Article reports the result of a computational study on the reaction of hydrazoic acid and trimethylindium (TMIn), coadsorbed on TiO 2 rutile (110) surface. The adsorption geometries and energies of possible adsorbates including HN 3 -In(CH 3 ) 3 (a) and its derivatives, HN 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 )(a), and N-In(a), have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. The mechanisms of these surface reactions have also been explicitly elucidated with the computed potential energy surfaces. Starting from the interaction of three stable HN 3 adsorbates, HN 3 -O b (a), H(N 2 )N-O b (a), and Ti-NN(H)N-O b (a), where O b is the bridged O site on the surface, with two stable intermediates from the adsorption and dissociative adsorption of TMIn, (H 3 C) 3 In-O b (a) and (H 3 C) 2 In-Ob(a) + H 3 C-O b (a), InN products can be formed exothermically via four reaction paths following the initial barrierless In-atom association with the N atom directly bonded to H, by CH 4 elimination (with ∼40 kcal/mol barriers), the InN-N bond breaking and the final CH 3 elimination or migration (with <20 kcal/mol barriers). These Langmuir - Hinshelwood processes producing the two most stable InN(a) side-on adsorptions confirm that HN 3 and TMIn are indeed very efficient precursors for the deposition of InN films on TiO 2 nanoparticles. The result of similar calculations for the reactions occurring by the Rideal - Eley mechanism involving HN 3 (a) + TMIn(g) and HN 3 (g) + TMIn(a) indicates that they are energetically less favored and produce the less stable InN(a) with end-on configurations.",
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N2 - This Article reports the result of a computational study on the reaction of hydrazoic acid and trimethylindium (TMIn), coadsorbed on TiO 2 rutile (110) surface. The adsorption geometries and energies of possible adsorbates including HN 3 -In(CH 3 ) 3 (a) and its derivatives, HN 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 )(a), and N-In(a), have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. The mechanisms of these surface reactions have also been explicitly elucidated with the computed potential energy surfaces. Starting from the interaction of three stable HN 3 adsorbates, HN 3 -O b (a), H(N 2 )N-O b (a), and Ti-NN(H)N-O b (a), where O b is the bridged O site on the surface, with two stable intermediates from the adsorption and dissociative adsorption of TMIn, (H 3 C) 3 In-O b (a) and (H 3 C) 2 In-Ob(a) + H 3 C-O b (a), InN products can be formed exothermically via four reaction paths following the initial barrierless In-atom association with the N atom directly bonded to H, by CH 4 elimination (with ∼40 kcal/mol barriers), the InN-N bond breaking and the final CH 3 elimination or migration (with <20 kcal/mol barriers). These Langmuir - Hinshelwood processes producing the two most stable InN(a) side-on adsorptions confirm that HN 3 and TMIn are indeed very efficient precursors for the deposition of InN films on TiO 2 nanoparticles. The result of similar calculations for the reactions occurring by the Rideal - Eley mechanism involving HN 3 (a) + TMIn(g) and HN 3 (g) + TMIn(a) indicates that they are energetically less favored and produce the less stable InN(a) with end-on configurations.

AB - This Article reports the result of a computational study on the reaction of hydrazoic acid and trimethylindium (TMIn), coadsorbed on TiO 2 rutile (110) surface. The adsorption geometries and energies of possible adsorbates including HN 3 -In(CH 3 ) 3 (a) and its derivatives, HN 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 ) 2 (a), N 3 -In(CH 3 )(a), and N-In(a), have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. The mechanisms of these surface reactions have also been explicitly elucidated with the computed potential energy surfaces. Starting from the interaction of three stable HN 3 adsorbates, HN 3 -O b (a), H(N 2 )N-O b (a), and Ti-NN(H)N-O b (a), where O b is the bridged O site on the surface, with two stable intermediates from the adsorption and dissociative adsorption of TMIn, (H 3 C) 3 In-O b (a) and (H 3 C) 2 In-Ob(a) + H 3 C-O b (a), InN products can be formed exothermically via four reaction paths following the initial barrierless In-atom association with the N atom directly bonded to H, by CH 4 elimination (with ∼40 kcal/mol barriers), the InN-N bond breaking and the final CH 3 elimination or migration (with <20 kcal/mol barriers). These Langmuir - Hinshelwood processes producing the two most stable InN(a) side-on adsorptions confirm that HN 3 and TMIn are indeed very efficient precursors for the deposition of InN films on TiO 2 nanoparticles. The result of similar calculations for the reactions occurring by the Rideal - Eley mechanism involving HN 3 (a) + TMIn(g) and HN 3 (g) + TMIn(a) indicates that they are energetically less favored and produce the less stable InN(a) with end-on configurations.

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