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Title: Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis

Abstract

Ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments narrow the pressure and materials gaps between UHV surface science experiments and applications. Upon closing these gaps, ambiguity can enter the analysis of the spectra due to overlapping peaks from different elements or functional groups of both the sample and the gas phase. Additionally, reaction intermediates and mechanisms are often inaccessible from interpretation of APXPS data alone. In many cases, these issues can be overcome with the aid of density functional theory (DFT) calculations. Here, we outline our process of combining DFT calculations with APXPS experiments by describing our recent investigations of the adsorption of dimethyl methylphosphonate (DMMP) on MoO3 and CuO. We begin by showing the importance of the characterization of the isolated gas phase molecule before adsorption onto a surface. In particular, strong agreement between theory and experiment helps identify plausible decomposition pathways of the isolated molecule and provides a baseline for interpretation of spectra showing evidence of DMMP interaction with surfaces. The intact adsorption of DMMP on MoO3 offers an illustration of how moving beyond pristine single crystalline surfaces in calculations can enable better modeling of experimental trends that result from surface defects. Studies of DMMP adsorption on CuO exemplifymore » the powerful synergy of APXPS combined with DFT for elucidation of complex reaction mechanisms on surfaces.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [2];  [5]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of Maryland, College Park, MD (United States). Materials Science and Engineering Dept.
  3. Naval Research Lab. (NRL), Washington, DC (United States). Chemistry Division
  4. Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biology
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1543495
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 61; Journal Issue: 20; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
Chemistry

Citation Formats

Head, Ashley R., Trotochaud, Lena, Tsyshevsky, Roman, Fears, Kenan, Eichhorn, Bryan, Kuklja, Maija M., and Bluhm, Hendrik. Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis. United States: N. p., 2018. Web. doi:10.1007/s11244-018-1062-7.
Head, Ashley R., Trotochaud, Lena, Tsyshevsky, Roman, Fears, Kenan, Eichhorn, Bryan, Kuklja, Maija M., & Bluhm, Hendrik. Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis. United States. https://doi.org/10.1007/s11244-018-1062-7
Head, Ashley R., Trotochaud, Lena, Tsyshevsky, Roman, Fears, Kenan, Eichhorn, Bryan, Kuklja, Maija M., and Bluhm, Hendrik. Sat . "Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis". United States. https://doi.org/10.1007/s11244-018-1062-7.
@article{osti_1543495,
title = {Coupling Ambient Pressure X-ray Photoelectron Spectroscopy with Density Functional Theory to Study Complex Surface Chemistry and Catalysis},
author = {Head, Ashley R. and Trotochaud, Lena and Tsyshevsky, Roman and Fears, Kenan and Eichhorn, Bryan and Kuklja, Maija M. and Bluhm, Hendrik},
abstractNote = {Ambient pressure X-ray photoelectron spectroscopy (APXPS) experiments narrow the pressure and materials gaps between UHV surface science experiments and applications. Upon closing these gaps, ambiguity can enter the analysis of the spectra due to overlapping peaks from different elements or functional groups of both the sample and the gas phase. Additionally, reaction intermediates and mechanisms are often inaccessible from interpretation of APXPS data alone. In many cases, these issues can be overcome with the aid of density functional theory (DFT) calculations. Here, we outline our process of combining DFT calculations with APXPS experiments by describing our recent investigations of the adsorption of dimethyl methylphosphonate (DMMP) on MoO3 and CuO. We begin by showing the importance of the characterization of the isolated gas phase molecule before adsorption onto a surface. In particular, strong agreement between theory and experiment helps identify plausible decomposition pathways of the isolated molecule and provides a baseline for interpretation of spectra showing evidence of DMMP interaction with surfaces. The intact adsorption of DMMP on MoO3 offers an illustration of how moving beyond pristine single crystalline surfaces in calculations can enable better modeling of experimental trends that result from surface defects. Studies of DMMP adsorption on CuO exemplify the powerful synergy of APXPS combined with DFT for elucidation of complex reaction mechanisms on surfaces.},
doi = {10.1007/s11244-018-1062-7},
url = {https://www.osti.gov/biblio/1543495}, journal = {Topics in Catalysis},
issn = {1022-5528},
number = 20,
volume = 61,
place = {United States},
year = {2018},
month = {10}
}

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