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Title: Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid

Abstract

Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.

Authors:
 [1];  [1];  [2];  [2];  [2];  [3];  [4]
+ Show Author Affiliations
  1. Univ. of Manchester (United Kingdom)
  2. Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
  3. Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy; Freie Univ. Berlin, Berlin (Germany)
  4. Univ. of Manchester (United Kingdom); Univ. of Leeds, Leeds (United Kingdom)
Publication Date:
Research Org.:
Univ. of Manchester (United Kingdom)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC)
OSTI Identifier:
1343097
Grant/Contract Number:  
AC02-98CH10886; EP/1013563/1; 312284; 279344
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 21; Journal Issue: 19; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ionization potentials; liquids; X-ray scattering; speciation; X-ray absorption spectroscopy

Citation Formats

Stevens, Joanna S., Gainar, Adrian, Suljoti, Edlira, Xiao, Jie, Golnak, Ronny, Aziz, Emad F., and Schroeder, Sven L. M. Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid. United States: N. p., 2015. Web. doi:10.1002/chem.201405635.
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Stevens, Joanna S., Gainar, Adrian, Suljoti, Edlira, Xiao, Jie, Golnak, Ronny, Aziz, Emad F., & Schroeder, Sven L. M. Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid. United States. https://doi.org/10.1002/chem.201405635
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Stevens, Joanna S., Gainar, Adrian, Suljoti, Edlira, Xiao, Jie, Golnak, Ronny, Aziz, Emad F., and Schroeder, Sven L. M. Wed . "Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid". United States. https://doi.org/10.1002/chem.201405635. https://www.osti.gov/servlets/purl/1343097.
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@article{osti_1343097,
title = {Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p -Aminobenzoic Acid},
author = {Stevens, Joanna S. and Gainar, Adrian and Suljoti, Edlira and Xiao, Jie and Golnak, Ronny and Aziz, Emad F. and Schroeder, Sven L. M.},
abstractNote = {Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO–LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. Finally, this provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute–solvent interactions.},
doi = {10.1002/chem.201405635},
journal = {Chemistry - A European Journal},
number = 19,
volume = 21,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2015},
month = {Wed Mar 18 00:00:00 EDT 2015}
}
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https://doi.org/10.1002/chem.201405635
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    Works referencing / citing this record:

    A liquid flatjet system for solution phase soft-x-ray spectroscopy
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    • Structural Dynamics, Vol. 2, Issue 5
    • DOI: 10.1063/1.4928715
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