Surface-Plasmon-Induced Ammonia Decomposition on Copper: Excited-State Reaction Pathways Revealed by Embedded Correlated Wavefunction Theory

Junwei Lucas Bao, Emily Ann Carter

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Ammonia is a promising hydrogen storage medium; however, its decomposition via conventional thermal catalysis requires a significant amount of thermal energy input in order to overcome the reaction barriers. Here, we use embedded correlated wavefunction (ECW) theory to quantify reaction pathways and energetics for ammonia decomposition (N-H bond dissociation and N2 and H2 associative desorption) on copper (Cu) nanoparticles using a Cu (111) surface model. We predict that surface plasmon excitations will be able to facilitate ammonia decomposition by substantially reducing the effective barriers along excited-state pathways. We estimate the reductions in reaction barriers for breaking the first N-H bond and for recombinative desorption of surface-bound nitrogen and hydrogen atoms to be approximately 1.7, 0.8, and 0.5 eV, respectively. Further, by using the experimental N2 desorption barrier as a reference, we compare the accuracy of various theoretical methods, including plane-wave Kohn-Sham density functional theory calculations with commonly used exchange-correlation functionals, embedded complete active space second-order perturbation theory, and embedded multiconfiguration pair-density functional theory. This work offers further confirmation that the ECW theoretical framework is the most robust for treating highly correlated local electronic structures of solids.

Original languageEnglish (US)
Pages (from-to)9944-9957
Number of pages14
JournalACS Nano
Volume13
Issue number9
DOIs
StatePublished - 2019

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Engineering(all)
  • Physics and Astronomy(all)

Keywords

  • ammonia decomposition
  • embedded correlated wavefunction theory
  • hydrogen associative desorption
  • localized surface plasmon resonance
  • nitrogen associative desorption
  • photocatalysis

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