Infrared spectrum of potassium‐cationized triethylphosphate generated using tandem mass spectrometry and infrared multiple photon dissociation

Abstract

Tandem mass spectrometry and wavelength-selective infrared photodissociation were used to generate an infrared spectrum of gas-phase triethylphosphate cationized by attachment of K(+). Prominent absorptions were observed in the region of 900 to 1300 cm(-1) that are characteristic of phosphate P=O and P-O-R stretches. The relative positions and intensities of the IR absorptions were reproduced well by density functional theory (DFT) calculations performed using the B3LYP functional and the 6-31+G(d), 6-311+G(d,p) and 6-311++G(3df,2pd) basis sets. Because of good correspondence between experiment and theory for the cation, DFT was then used to generate a theoretical spectrum for neutral triethylphosphate, which in turn accurately reproduces the IR spectrum of the neat liquid when solvent effects are included in the calculations.

Lithium Alanates as Negative Electrodes in Lithium‐Ion Batteries

“…On the other hand, the appearance of bands at about $\tilde \nu $ =1270, 1000, 850, and 780 cm −1 suggests the parallel formation of organic phosphates [i.e. F 3− x (RO) x PO] 34. 35 Below $\tilde \nu $ =700 cm −1 , a few other weak bands are observed: these are likely related to the phosphate PF 2 bending mode as well as AlO stretching and bending 36.…”

Infrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Triethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure

“…Structures and spectra were reported by Groenewold and coworkers for the neutral TEP system as previously mentioned [50]. To provide a useful evaluation of the results of their work, an IR spectrum of neat TEP from the National Institute of Standards and Technology (NIST) spectral database [55] was compared with a DFT predicted spectra [B3LYP/6-311++g(3df, 2pd)] that accounted for solvent effects through the use of the integral-equation-formalism polarizable continuum model (IEFPCM).…”

“…In addition to its use as a simple model of phosphate esters found in nucleotides and nucleic acid chains, TEP is a strong Lewis base prized for its ability to extract U(VI) and Pu(IV) from nitric acid that has been obtained from spent nuclear fuel rods [50,51]. In the work of Groenewold et al [50], potassium cationized TEP was investigated using methods similar to those employed in the current work.…”

Solvent Reorganization and Additives Synergistically Enable High-Performance Na-Ion Batteries

“…Figure f shows the PO stretching band from TEP molecules in different TEP–PhCF 3 mixed solvents. In pure TEP solvent, two peaks at 1260 and 1271 cm –1 are assigned to the PO stretching of TEP in C 3 v and C 3 conformers, respectively. − The Mulliken atomic charge indicates the presence of a hydrogen bond interaction between an alkyl hydrogen and phosphoryl oxygen of TEP in the C 3 v conformer (Figure S1a and Table S5); thus, the C 3 v conformer of TEP presents a lower PO frequency than the C 3 conformer (Figure f) . As the proportion of PhCF 3 increases in the mixed solvents, the intensity of the C 3 v conformer of PO decreases while the intensity of the C 3 conformer of PO increases, and both peaks continuously move to higher frequencies.…”