Quarantined Cc-stretched Formic Acid: Molecular Work-out In (self) Isolation

Meyer, Katharina A. E.

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https://hdl.handle.net/2142/116617 Copy

Description

Title

Quarantined Cc-stretched Formic Acid: Molecular Work-out In (self) Isolation

Author(s)

Meyer, Katharina A. E.

Contributor(s)

Nejad, Arman

Issue Date

2022-06-21

Keyword(s)

Mini-symposium: Benchmarking in Spectroscopy

Abstract

Vibrational spectra of small molecules effectively probe the underlying potential energy hypersurface, which can be tested when combined with accurate anharmonic calculations.\footnote{P. R. Franke, J. F. Stanton, G. E. Douberly, \textit{J. Phys. Chem. A} \textbf{2021}, \textit{125}, 1301--1324; J. M. Bowman, T. Carrington, H.-D. Meyer, \textit{Mol. Phys.} \textbf{2008}, \textit{106}, 2145--2182.} Particularly suited for a performance test of quantum chemical gas phase calculations are spectra recorded in a supersonic expansion, as significant rotational cooling is achieved while the molecules or molecular clusters remain isolated in the gas phase. One of the smallest reference systems for such a benchmarking study is the formic acid monomer with its $cis$-$trans$-torsional isomerism.\footnote{D. P. Tew, W. Mizukami, \textit{J. Phys. Chem. A} \textbf{2016}, \textit{120}, 9815--9828; F. Richter, P. Carbonni\`{e}re, \textit{J. Chem. Phys.} \textbf{2018}, \textit{148}, 064303; A. Nejad, E. L. Sibert III, \textit{J. Chem. Phys.} \textbf{2021}, \textit{154}, 064301.} Recently, new vibrational reference data on the stretching vibrations of all four H/D isotopologues of the higher-energy $cis$-conformer were provided $via$ the combination of Raman jet spectroscopy with thermal excitation.\footnote{A. Nejad , M. A. Suhm, K. A. E. Meyer, \textit{Phys. Chem. Chem. Phys.} \textbf{2020}, \textit{22}, 25492--25501.} Another very interesting carboxylic acid for such a study is the smallest acetylenic acid, HCC-COOH, whose $cis$- and $trans$-rotamers will be discussed in this contribution. Of particular interest are two almost isoenergetic $trans$-fundamentals of different symmetry which are shown to be a particularly useful benchmarking target, but also the dimers of the CC-stretched formic acid prove to be an insightful reference system for benchmarking.\footnote{K. A. E. Meyer, A. Nejad, \textit{Phys. Chem. Chem. Phys.} \textbf{2021}, \textit{23}, 17208--17223.}

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Handle URL

https://hdl.handle.net/2142/116617&&

DOI

https://doi.org/10.15278/isms.2022.TI08

Copyright and License Information

Copyright 2022 held by the authors

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