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Title: Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate

Dimethyl methylphosphonate (DMMP) is one of the most widely used molecules to simulate chemical warfare agents in adsorption experiments. However, the details of the electronic structure of the isolated molecule have not yet been reported. Here, we have directly probed the occupied valence and core levels using gas phase photoelectron spectroscopy and the unoccupied states using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Density functional theory (DFT) calculations were used to study the electronic structure, assign the spectral features, and visualize the molecular orbitals. Comparison with parent molecules shows that valence and core-level binding energies of DMMP follow trends of functional group substitution on the P center. The photoelectron and NEXAFS spectra of the isolated molecule will serve as a reference in studies of DMMP adsorbed on surfaces.
Authors:
 [1] ;  [2] ;  [1] ;  [3] ;  [2] ;  [1]
  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
  3. Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Grant/Contract Number:
AC02-05CH11231; HDTRA11510005; DMR-130077
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 12; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOD; National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1465401

Head, Ashley R., Tsyshevsky, Roman, Trotochaud, Lena, Eichhorn, Bryan, Kuklja, Maija M., and Bluhm, Hendrik. Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate. United States: N. p., Web. doi:10.1021/acs.jpca.6b01098.
Head, Ashley R., Tsyshevsky, Roman, Trotochaud, Lena, Eichhorn, Bryan, Kuklja, Maija M., & Bluhm, Hendrik. Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate. United States. doi:10.1021/acs.jpca.6b01098.
Head, Ashley R., Tsyshevsky, Roman, Trotochaud, Lena, Eichhorn, Bryan, Kuklja, Maija M., and Bluhm, Hendrik. 2016. "Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate". United States. doi:10.1021/acs.jpca.6b01098. https://www.osti.gov/servlets/purl/1465401.
@article{osti_1465401,
title = {Electron Spectroscopy and Computational Studies of Dimethyl Methylphosphonate},
author = {Head, Ashley R. and Tsyshevsky, Roman and Trotochaud, Lena and Eichhorn, Bryan and Kuklja, Maija M. and Bluhm, Hendrik},
abstractNote = {Dimethyl methylphosphonate (DMMP) is one of the most widely used molecules to simulate chemical warfare agents in adsorption experiments. However, the details of the electronic structure of the isolated molecule have not yet been reported. Here, we have directly probed the occupied valence and core levels using gas phase photoelectron spectroscopy and the unoccupied states using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Density functional theory (DFT) calculations were used to study the electronic structure, assign the spectral features, and visualize the molecular orbitals. Comparison with parent molecules shows that valence and core-level binding energies of DMMP follow trends of functional group substitution on the P center. The photoelectron and NEXAFS spectra of the isolated molecule will serve as a reference in studies of DMMP adsorbed on surfaces.},
doi = {10.1021/acs.jpca.6b01098},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 12,
volume = 120,
place = {United States},
year = {2016},
month = {3}
}