Microwave And Computational Studies Of Hydrated Acid Anhydrides: Capturing A Local Potential Energy Minimum And Exploring The Effect Of C(ch₃)₃ And Cf₃ Substituents

Love, Nathan

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https://hdl.handle.net/2142/111611 Copy

Description

Title

Microwave And Computational Studies Of Hydrated Acid Anhydrides: Capturing A Local Potential Energy Minimum And Exploring The Effect Of C(ch₃)₃ And Cf₃ Substituents

Author(s)

Love, Nathan

Contributor(s)

• Leopold, Kenneth R.
• Huff, Anna

Issue Date

2021-06-23

Keyword(s)

Large molecules

Abstract

Microwave studies of hydrated acid anhydrides (RCOOCOR-H$_{2}$O) provide an interesting venue for characterizing local minima on the potential energy landscape of reactive systems. This talk reports the microwave spectra of the monohydrates of pivalic anhydride (R = R' = C(CH$_{3}$)$_{3}$), trifluoracetic anhydride (R = R' = CF$_{3}$), and the mixed pivalic-trifluoroacetic anhydride (R = C(CH$_{3}$)$_{3}$, R' = CF$_{3}$). While the ultimate fate of these species in bulk aqueous solution is hydrolysis to form the parent acids, this work captures the precursor complexes and investigates the effect of R and R' on the geometry of the monohydrate. Microwave spectra of the parent species and their D$_{2}$O and DOH isotopologues are reported, as is an in-depth computational analysis at different levels of theory. Calculated structures show varying degrees of hydrogen bonding and electrophilic-nucleophilic interaction, depending on the particular combination of R and R' groups. Additionally, closely spaced pairs of tunneling states arising from internal water motion were observed in the monohydrate spectra except in the case where R = R' = CF$_{3}$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Permalink

http://hdl.handle.net/2142/111611

DOI

10.15278/isms.2021.WL12

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