Unveiling the coexistence of cis- and trans-isomers in the hydrolysis of ZrO2: A coupled DFT and high-resolution photoelectron spectroscopy study

High-resolution anion photoelectron spectroscopy of the ZrO3H2- and ZrO3D2- anions and complementary electronic structure calculations are used to investigate the reaction between zirconium dioxide and a single water molecule, ZrO20/- + H2O. Experimental spectra of ZrO3H2- and ZrO3D2- were obtained using slow photoelectron velocity-map imaging (cryo-SEVI), revealing the presence of two dissociative adduct conformers and yielding insight into the vibronic structure of the corresponding neutral species. Franck-Condon simulations for both the \textit{cis}-- and \textit{trans}--dihydroxide structures are required to fully reproduce the experimental spectrum. Additionally, it was found that water-splitting is stabilized more by ZrO2 than TiO2, suggesting Zr-based catalysts are more reactive toward hydrolysis.

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Unveiling the Coexistence of Cis and Trans Isomers in the Hydrolysis of ZrO2: A Coupled DFT and High-Resolution Photoelectron Spectroscopy Study

10.26434/chemrxiv.13177130.v2 ◽

2020 ◽

Author(s):

Ali Abou Taka ◽

Mark Babin ◽

Xianghai Sheng ◽

Jessalyn DeVine ◽

Daniel Neumark ◽

...

Keyword(s):

High Resolution ◽

Photoelectron Spectroscopy ◽

Experimental Spectrum ◽

Velocity Map Imaging ◽

Cis And Trans Isomers ◽

Single Water Molecule ◽

Anion Photoelectron Spectroscopy ◽

Cis And Trans ◽

Franck Condon ◽

Hydrolysis Of

High-resolution anion photoelectron spectroscopy of the ZrO3H2- and ZrO3D2- anions and complementary electronic structure calculations are used to investigate the reaction between zirconium dioxide and a single water molecule, ZrO20/- + H2O. Experimental spectra of ZrO3H2- and ZrO3D2- were obtained using slow photoelectron velocity-map imaging (cryo-SEVI), revealing the presence of two dissociative adduct conformers and yielding insight into the vibronic structure of the corresponding neutral species. Franck-Condon simulations for both the \textit{cis}-- and \textit{trans}--dihydroxide structures are required to fully reproduce the experimental spectrum. Additionally, it was found that water-splitting is stabilized more by ZrO2 than TiO2, suggesting Zr-based catalysts are more reactive toward hydrolysis.

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Uncovering the coexistence of stereoisomers isomers in the hydrolysis of ZrO2: A coupled DFT and high-resolution photoelectron spectroscopy study

10.1021/scimeetings.1c01355 ◽

2021 ◽

Author(s):

Ali Abou Taka ◽

Mark Babin ◽

Xianghai Sheng ◽

Jessalyn Devine ◽

Daniel Neumark ◽

...

Keyword(s):

High Resolution ◽

Photoelectron Spectroscopy ◽

Spectroscopy Study ◽

Hydrolysis Of

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ZEKE Photoelectron Spectroscopy of the cis and trans Isomers of Formanilide

Angewandte Chemie International Edition ◽

10.1002/1521-3773(20020104)41:1<166::aid-anie166>3.0.co;2-3 ◽

2002 ◽

Vol 41 (1) ◽

pp. 166-168 ◽

Cited By ~ 15

Author(s):

Susanne Ullrich ◽

György Tarczay ◽

Xin Tong ◽

Caroline E. H. Dessent ◽

Klaus Müller-Dethlefs

Keyword(s):

Photoelectron Spectroscopy ◽

Trans Isomers ◽

Cis And Trans Isomers ◽

Zeke Photoelectron Spectroscopy ◽

Cis And Trans

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Vinyl ether hydrolysis. XII. Use of cis–trans isomerism to probe the reaction mechanism

Canadian Journal of Chemistry ◽

10.1139/v78-074 ◽

1978 ◽

Vol 56 (4) ◽

pp. 461-464 ◽

Cited By ~ 12

Author(s):

Y. Chiang ◽

A. J. Kresge ◽

C. I. Young

Keyword(s):

Reaction Mechanism ◽

Vinyl Ether ◽

Hydrolysis Reaction ◽

Trans Isomers ◽

Vinyl Methyl ◽

Reaction Conditions ◽

Carbonium Ion ◽

Cis And Trans Isomers ◽

Cis And Trans ◽

Hydrolysis Of

Rates of hydrolysis of cis- and trans-β-phenylvinyl methyl ethers, cis- and trans-β-(p-nitrophenyl)vinyl methyl ethers, and cis- and trans-β-cyanovinyl ethyl ethers were measured in concentrated (10–55 wt%) aqueous perchloric acids. The results show that these cis and trans isomers do not interconvert under the hydrolysis reaction conditions, and that formation of the alkoxy carbonium ion intermediate in these reactions is therefore not reversible.

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The Effect of N-Substitution on the Rates of Saponification of Some Amino Acid Esters

Canadian Journal of Chemistry ◽

10.1139/v71-580 ◽

1971 ◽

Vol 49 (21) ◽

pp. 3468-3476 ◽

Cited By ~ 2

Author(s):

Jocelyn E. Purdie ◽

N. Leo Benoiton

Keyword(s):

Amino Acid ◽

Methyl Esters ◽

Activation Parameters ◽

Side Chain ◽

Amino Acid Esters ◽

Trans Isomers ◽

Cis And Trans Isomers ◽

Cis And Trans ◽

Hydrolysis Of ◽

Acid Esters

The saponification rates (measured at 25 ° by a titrimetric method) of the unprotonated forms of the methyl esters of glycine, alanine, leucine, valine, and phenylalanine were compared with those of the N-methyl, the N-acetyl, and the N-acetyl, N-methylamino acid analogues. N-Acetylation slightly increased or decreased the rate but N-methylation caused a reduction by as much as a factor of ten, depending on the complexity of the side-chain. The esters of the N-acetyl, N-methylamino acids, which exist as cis and trans isomers, were saponified at rates intermediate between those of the esters of the N-acetylamino acids and N-methylamino acids. Activation parameters were obtained for the phenylalanine and leucine derivatives. N-Methylation resulted in an increase in ΔH≠ and ΔS≠ which was attributed in part to solvation effects. The hydrolysis of the cationic esters of glycine and alanine was still evident at pH 11.0. N-Methylation had little effect on the rates of saponification of the charged forms.

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