Elucidation of the electronic states in polyethylene glycol by attenuated Total reflectance spectroscopy in the far-ultraviolet region

Ueno, Nami; Wakabayashi, Tomonari; Morisawa, Yusuke

doi:10.1016/j.saa.2018.01.042

Cited by 9 publications

(11 citation statements)

References 30 publications

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“…A shoulder band at around 177 nm disappeared in both solutions at [Li + ]0/[COC]0 = 0.063. As previously described, 11 PEG shows three transitions corresponding to n(OH)-Ryd 3p, n(COC)-Ryd 3p, and n(COC)-Ryd 3s at approximately 155, 163, and 177 nm, respectively. An ATR-FUV spectrum between 145 and 300 nm was also obtained for the pure solvent (Fig.…”

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confidence: 65%

“…We recently developed attenuated total reflectance spectroscopy in the far-ultraviolet region (ATR-FUV) 9,10 and successfully applied this technique to observe the electronic transitions of polyether in the wavelength range 145 -190 nm. 11 When varying the concentration of Li + in the polyether, we observed concentration-dependent effects in the ATR-FUV spectra, which indicated changes in the electronic states of the polyether. We observed a reflection absorbance at approximately 170 nm due to an n-Rydberg (Ryd) 3s transition, which was correlated to a concentration of oxygen in ether not involved in a coordination bond.…”

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confidence: 78%

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Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

2019

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Attenuated total reflectance-far ultraviolet (ATR-FUV) spectra of Li + and polyether ligands, such as glymes and poly (ethylene glycol) (PEG), in solution give information about changes in the electronic states of the ligands. From the ATR-FUV spectra, the coordination numbers between Li + and monoglyme, diglyme, triglyme, and PEG400 were determined to be 4, 5, 6, and 5, respectively. Our results indicate that Li + is coordinated only by the ligands rather than its counter-ions.

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confidence: 65%

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confidence: 78%

Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

2019

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“…As demonstrated in these studies, the transition energy of each n to 3s, 3p, or 3d Ryd transition is not strongly related to the functional groups, but the relative intensities are affected. Polymers also show n –Ryd transitions . In fact, we have previously reported the assignment of the electronic transitions of PEG, based on a comparison of experimental and calculated results for their dependence on molecular weight .…”

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confidence: 99%

Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li⁺, Studied by ATR Far-Ultraviolet Spectroscopy

et al. 2019

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This study investigates the electronic transitions of complexes of lithium with polyethylene glycol (PEG) by the absorption bands of solvent molecules via attenuated total reflectance spectroscopy in the far-UV region (ATR−FUV). Alkali-metal complexes are interesting materials because of their functional characteristics such as good ionic conductivity. These complexes are used as polymer electrolytes for Li batteries and as one of the new types of room-temperature ionic liquids, termed solvation ionic liquids. Considering these applications, alkali-metal complexes have been studied mainly for their electrochemical characteristics; there is no fundamental study providing a clear understanding of electronic states in terms of electronic structures for the ground and excitation states near the highest occupied molecular orbital− lowest occupied molecular orbital transitions. This study explores the electronic transitions of ligand molecules in alkali-metal complexes. In the ATR−FUV spectra of the Li−PEG complex, a decrease in intensity and a large blue shift (over 4 nm) were observed to result from an increase in the concentration of Li salts. This observation suggests the formation of a complex, with coordinate bonding between Li + and the O atoms in PEG. Comparison of the experimental spectrum with a simulated spectrum of the Li−PEG complex calculated by time-dependent density functional theory indicated that changes in the intensities and peak positions of bands at approximately 155 and 177 nm (pure PEG shows bands at 155, 163, and 177 nm) are due to the formation of coordinate bonding between Li + and the O atoms in the ether molecule. The intensity of the 177 nm band depends on the number of residual free O atoms in the ether, and the peak wavelength at approximately 177 nm changes with the expansion of the electron clouds of PEG. We assign a band in the 145−155 nm region to the alkali-metal complex because we observed a new band at approximately 150 nm in the ATR−FUV spectra of very highly concentrated binary mixtures.

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“…Morisawa et al focused on the electronic states of polymers such as nylon, 16 polyethylene glycol (PEG), 17 polyhydroxy butylate (PHB), nanocomposites of PHB and graphene, 18 and complexes of PEG and lithium ions. 19,20 In these studies, the electronic transitions of polymers were investigated by comparing the ATR-FUV spectra and simulated spectra obtained using quantum chemical calculations, thus revealing the potential usefulness of ATR-FUV for polymer analysis.…”

Section: Introductionmentioning

confidence: 99%

“…This study revealed that, even for electronic transitions, each atomic group exhibited independent transitions. In another study, alkali metal complexes composed of a Li salt and PEG were investigated, and it was found that the absorption bands of PEG 17 at 155 and 177 nm shifted higher in energy because of the formation of a complex between Li þ ions and PEG. 19 Further, the intensity of the band at 177 nm decreased with increasing Li salt concentration.…”

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confidence: 99%

Attenuated Total Reflection–Far-Ultraviolet Spectroscopy and Quantum Chemical Calculations of the Electronic Structure of the Top Surface and Bulk of Polyethylenes with Different Crystallinities

et al. 2021

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In this study, we explored the electronic structure of the surfaces of polyethylene samples having different crystallinities using attenuated total reflection (ATR)-far-ultraviolet (FUV) spectroscopy and quantum chemical calculations. Specifically, the ATR-FUV spectra of five types of high-density polyethylene (HDPE), six types of linear low-density PE (LLDPE), and seven types of low-density PE (LDPE) were obtained. All the spectra contained an intense band near 156 nm and a broad band between 180 and 190 nm. Transmission spectra were obtained for the thin-film (30 Î¼m) PE samples between 165 and 250 nm. In this region, the HDPE films show very low-intensity bands. In contrast, the transmission spectra of the LLDPE and LDPE samples yielded weak-to-medium and medium-intensity bands around 180â190 nm, respectively. In addition, to understand the differences in the absorption spectra among the PEs observed, we simulated the spectra of <i>n</i>-pentane as a PE crystal model using time-dependent density functional theory and found that the common intense band at 156 nm is due to the Ï (C(2p)-H)âRydberg 3s, 3p transition. The absorption bands near 180â190 nm may correspond to aggregates of numerous molecular chains in the amorphous parts of the LLDPE and LDPE samples.

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Elucidation of the electronic states in polyethylene glycol by attenuated Total reflectance spectroscopy in the far-ultraviolet region

Cited by 9 publications

References 30 publications

Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li⁺, Studied by ATR Far-Ultraviolet Spectroscopy

Attenuated Total Reflection–Far-Ultraviolet Spectroscopy and Quantum Chemical Calculations of the Electronic Structure of the Top Surface and Bulk of Polyethylenes with Different Crystallinities

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Elucidation of the electronic states in polyethylene glycol by attenuated Total reflectance spectroscopy in the far-ultraviolet region

Cited by 9 publications

References 30 publications

Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

Determining the Coordination Number of Li+ and Glyme or Poly(ethylene glycol) in Solution Using Attenuated Total Reflectance-Far Ultraviolet Spectroscopy

Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li+, Studied by ATR Far-Ultraviolet Spectroscopy

Attenuated Total Reflection–Far-Ultraviolet Spectroscopy and Quantum Chemical Calculations of the Electronic Structure of the Top Surface and Bulk of Polyethylenes with Different Crystallinities

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Changes in the Electronic Transitions of Polyethylene Glycol upon the Formation of a Coordinate Bond with Li⁺, Studied by ATR Far-Ultraviolet Spectroscopy