Excess Proton Hydrate Structures with Large Proton Polarizability, Screened by Tris(2-ethylhexyl) Phosphate

Brzeziński, Bogumił; Bartl, Franz; Zuńdel, Georg

doi:10.1021/jp9702762

Cited by 17 publications

(8 citation statements)

References 16 publications

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“…In the Naph-W complex, a strong O–H (Naph) ···O (W) hydrogen bond (of 1.810 Å, at the MP2/cc-pVDZ level), connects two molecules. Our calculated value of the hydrogen bond length (1.810 Å) is slightly longer than the value of 1.783 Å reported by Yoshino et al (at the RI-MP2/6-31G level of calculation). By increasing the number of water molecules, significantly shortening of OH (Naph) ···O(w) hydrogen-bond has been predicted in [Naph-W 3 ] complex (from 1.810 Å in Naph-W 1 to 1.636 Å in [Naph-W 3 ]).…”

Section: Results and Discussioncontrasting

confidence: 76%

Electronically Excited States of Neutral, Protonated α-Naphthol and Their Water Clusters: A Theoretical Study

et al. 2015

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The RI-MP2 and RI-CC2 methods have been employed to determine the potential energy profiles of neutral and protonated α-naphthol, in their individual forms and microhydrated with 1 and 3 water molecules, at different electronic states. According to calculated results, it has been predicted that dynamics of nonradiative processes in protonated α-naphthol is essentially different from that of its neutral homologue. In protonated α-naphthol, the calculations reveal that (1)σπ* state, is the most important photophysical state, having a bound nature with a broad potential curve along the OH coordinate of isolated system, while it is dissociative in monohydrated homologue. In neutral system, similar to phenol, the (1)πσ* state, plays the fundamental relaxation role along the O-H stretching coordinate. Moreover, microhydration strongly affects the photophysical properties of α-naphthol, mostly by alteration of the (1)ππ* PE profile, from a bound state in an isolated analogue to a dissociative state in hydrated systems. Furthermore, it has been found that three water molecules are necessary for ground state proton transfer between protonated α-naphthol and water; with a small barrier; (ΔE< 0.1 eV).

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Section: Results and Discussioncontrasting

confidence: 76%

Electronically Excited States of Neutral, Protonated α-Naphthol and Their Water Clusters: A Theoretical Study

et al. 2015

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“…In the tetrahydrated complex of PhH + , although the CC2 geometry optimization at 1 ππ* does not show significant geometry alterations, at the 1 A′′ ( 1 σπ*) state, the excited-state hydrogen/proton detachment along the phenolic OH bond coordinate has been predicted. As shown in Figure , the transferred hydrogen/proton has been attracted by two water molecules, producing a Zundel structure by sharing the excess proton between two neighboring water molecules.…”

Section: Resultsmentioning

confidence: 99%

Microhydration Effects on the Electronic Properties of Protonated Phenol: A Theoretical Study

Ataelahi

Omidyan

2013

J. Phys. Chem. A

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The CC2 (second-order approximate coupled cluster method) has been employed to investigate microhydration effect on electronic properties of protonated phenol (PhH(+)) According to the CC2 calculation results on electronic excited states of microhydrated PhH(+), for the S1 and S2 electronic states, which are of (1)ππ* nature and belong to the A' representation of molecular Cs point group, a significant blue shift effect on the S1 and S2 electronic states, which are of 1ππ* nature and belong to the A' representation of molecular Cs point group, in comparison to corresponding transitions on bare cation (PhH(+)), has been predicted. Nevertheless, for the S3-S0 (1A'', 1σπ*) transition, a large red shift effect has been predicted. Furthermore, it has been found that the lowest (1)σπ* state plays a prominent role in the photochemistry of these systems. In the bare protonated phenol, the (1)σπ* state is a bound state with a broad potential curve along the OH stretching coordinate, while it is dissociative in microhydrated species. This indicates to a predissociation of the S1((1)ππ*) state by a low-lying (1)σπ* state, which leads the excited system to a concerted proton-transfer reaction from protonated chromophore to the solvent. The dissociative (1)σπ* state in monohydrated PhH(+) has small barrier, while increasing the solvent molecules up to three removes the barrier and consequently expedites the proton-transfer reaction dynamics.

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“…The complexation of H + AuCl 4by neutral phosphates has been observed with tris(2ethylhexyl)phosphate and is due to the ability of the phosphoryl oxygen to hydrogen bond with the H + . 19 Linearity in the D vs σ correlation indicates that the polarizability of the divalent transition metal ion is a dominant variable in determining affinity. An increasing slope indicates increasing selectivity.…”

Section: Discussionmentioning

confidence: 99%

“…Protonation of the phosphoryl oxygen allows for complexation of FeCl 4 - , following the same mechanism as that for complexation of the Au(III) anion. The complexation of H + AuCl 4 - by neutral phosphates has been observed with tris(2-ethylhexyl)phosphate and is due to the ability of the phosphoryl oxygen to hydrogen bond with the H + …”

Section: Discussionmentioning

confidence: 99%

Bifunctional Coordinating Polymers: Auxiliary Groups as a Means of Tuning the Ionic Affinity of Immobilized Phosphate Ligands

Alexandratos

Zhu

2005

Macromolecules

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A series of coordinating polymers are synthesized by immobilizing polyols (ethylene glycol, glycerol, 1,1,1-tris(hydroxymethyl)ethane, pentaerythritol, and pentaerythritol triethoxylate) onto cross-linked poly(vinylbenzyl chloride) and then monosubstituting with diethyl phosphate ligands. Ionic affinities are determined with a series of divalent transition metal ions: Pb2+, Cd2+, Cu2+, Ni2+, and Zn2+. For each polymer, the variable controlling the affinity, as measured by the distribution coefficient, D, is the polarizability of the transition metal ion, as measured by the Misono softness parameter, σ. For D ≥ 0, the correlation is D = Sσ + σmin, where S is the selectivity and σmin is the minimum softness of a divalent transition metal ion which must be exceeded for coordination to occur. The values of S are 3810 (pentaerythritol), 1480 (pentaerythritol triethoxylate), 1340 (glycerol), 474 (tris(hydroxymethyl)ethane), and 21 (glycol); increasing S indicates greater selectivity. It is proposed that, though coordination occurs through the phosphate ligand, selectivity varies as a function of the polyol: the −OH groups act as auxiliary groups in modifying the polarizability of the phosphate ligands (the primary ligand) through hydrogen bonding and, as a result, affecting the selectivity of the primary ligand. Interaction between the −OH and phosphate moieties is evident in FTIR spectra of the polymers with the absorbance of a band within the range 874−895 cm-1.

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Excess Proton Hydrate Structures with Large Proton Polarizability, Screened by Tris(2-ethylhexyl) Phosphate

Cited by 17 publications

References 16 publications

Electronically Excited States of Neutral, Protonated α-Naphthol and Their Water Clusters: A Theoretical Study

Electronically Excited States of Neutral, Protonated α-Naphthol and Their Water Clusters: A Theoretical Study

Microhydration Effects on the Electronic Properties of Protonated Phenol: A Theoretical Study

Bifunctional Coordinating Polymers: Auxiliary Groups as a Means of Tuning the Ionic Affinity of Immobilized Phosphate Ligands

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