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Title: Photoelectron spectroscopy of solvated dicarboxylate and alkali metal ion clusters, M +[O 2C(CH 2) 2CO 2] 2-[H 2O] n(M = Na, K; n = 1–6)

Abstract

We present the results of combined experimental photoelectron spectroscopy and theoretical modeling studies of solvated dicarboxylate species ( -O 2C(CH 2)2CO 2 -, DC 22 -) in complex with Na + and K + metal cations. These ternary clusters can serve as a simple representative of models, in which ion and solute specific effects that play an important role in biological systems are prevalent. The experimental spectra of both Na + and K + show the presence of one major broad band that gradually shifts to higher electron binding energy (EBE) with increasing number of waters. For the Na+ case, using ab-initio calculations we have been able to obtain ground state structures that match well experimental EBE values. In the solvation range investigated in this work (up to 6 waters), Na+ retains direct contact with the dicarboxylate species and solvation shell is built in a fairly predictable fashion with the emphasis on the coordination of the negatively charged carboxylate groups accompanied by simultaneous coordination of metal cation. Up to 9 waters, theoretical predictions show that the solvent separated ion pair structure model starts appear albeit with a higher energy than the contact ion pair model. In addition to the mainmore » peak, Na +(DC 22 -)(H 2O)n clusters show development of a weak band at lower EBE when the number of water increases to 3. Similar phenomenon is observed for K + at a higher number of waters (n = 5). The origin of the band cannot be precisely identified. However, ab-initio calculations point out the existence of quaternary complex involved Na +/K +, H 2O, OH - and singly protonated dicarboxylate anion (HO 2C(CH) 2CO 2 -). Such complex appears to be stabilized at the solvation range corresponding to the appearance of the low EBE band and does match its peak, even though the energy of such complex is fairly high compared to the ternary clusters.« less

Authors:
 [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [2]
  1. College of Environmental and Chemical Engineering; Xi’an Polytechnic University; Xi’an; China; Physical Sciences Division
  2. Physical Sciences Division; Pacific Northwest National Laboratory; Washington 99352; USA
  3. Environmental Molecular Sciences Laboratory; Pacific Northwest National Laboratory; Washington 99352; USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1497070
Report Number(s):
PNNL-SA-135806
Journal ID: ISSN 1463-9076; PPCPFQ
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 46; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Li, Ren-Zhong, Deng, Shihu H. M., Hou, Gao-Lei, Valiev, Marat, and Wang, Xue-Bin. Photoelectron spectroscopy of solvated dicarboxylate and alkali metal ion clusters, M+[O2C(CH 2)2CO2]2-[H2O]n(M = Na, K; n = 1–6). United States: N. p., 2018. Web. doi:10.1039/c8cp03896a.
Li, Ren-Zhong, Deng, Shihu H. M., Hou, Gao-Lei, Valiev, Marat, & Wang, Xue-Bin. Photoelectron spectroscopy of solvated dicarboxylate and alkali metal ion clusters, M+[O2C(CH 2)2CO2]2-[H2O]n(M = Na, K; n = 1–6). United States. doi:10.1039/c8cp03896a.
Li, Ren-Zhong, Deng, Shihu H. M., Hou, Gao-Lei, Valiev, Marat, and Wang, Xue-Bin. Mon . "Photoelectron spectroscopy of solvated dicarboxylate and alkali metal ion clusters, M+[O2C(CH 2)2CO2]2-[H2O]n(M = Na, K; n = 1–6)". United States. doi:10.1039/c8cp03896a.
@article{osti_1497070,
title = {Photoelectron spectroscopy of solvated dicarboxylate and alkali metal ion clusters, M+[O2C(CH 2)2CO2]2-[H2O]n(M = Na, K; n = 1–6)},
author = {Li, Ren-Zhong and Deng, Shihu H. M. and Hou, Gao-Lei and Valiev, Marat and Wang, Xue-Bin},
abstractNote = {We present the results of combined experimental photoelectron spectroscopy and theoretical modeling studies of solvated dicarboxylate species (-O2C(CH2)2CO2-, DC22-) in complex with Na+ and K+ metal cations. These ternary clusters can serve as a simple representative of models, in which ion and solute specific effects that play an important role in biological systems are prevalent. The experimental spectra of both Na+ and K+ show the presence of one major broad band that gradually shifts to higher electron binding energy (EBE) with increasing number of waters. For the Na+ case, using ab-initio calculations we have been able to obtain ground state structures that match well experimental EBE values. In the solvation range investigated in this work (up to 6 waters), Na+ retains direct contact with the dicarboxylate species and solvation shell is built in a fairly predictable fashion with the emphasis on the coordination of the negatively charged carboxylate groups accompanied by simultaneous coordination of metal cation. Up to 9 waters, theoretical predictions show that the solvent separated ion pair structure model starts appear albeit with a higher energy than the contact ion pair model. In addition to the main peak, Na+(DC22-)(H2O)n clusters show development of a weak band at lower EBE when the number of water increases to 3. Similar phenomenon is observed for K+ at a higher number of waters (n = 5). The origin of the band cannot be precisely identified. However, ab-initio calculations point out the existence of quaternary complex involved Na+/K+, H2O, OH- and singly protonated dicarboxylate anion (HO2C(CH)2CO2-). Such complex appears to be stabilized at the solvation range corresponding to the appearance of the low EBE band and does match its peak, even though the energy of such complex is fairly high compared to the ternary clusters.},
doi = {10.1039/c8cp03896a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 46,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}