New Jet-cooled Vibrational Spectroscopic Benchmark Data Of The Cyclic Dimer And Trimer Of Formic Acid

Nejad, Arman

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https://hdl.handle.net/2142/116845 Copy

Description

Title

New Jet-cooled Vibrational Spectroscopic Benchmark Data Of The Cyclic Dimer And Trimer Of Formic Acid

Author(s)

Nejad, Arman

Contributor(s)

• Suhm, Martin A.
• Meyer, Katharina A. E.

Issue Date

2022-06-23

Keyword(s)

Mini-symposium: Benchmarking in Spectroscopy

Abstract

\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.6]{F_FF_FAD_in_FFF_v2.eps} \end{wrapfigure} Using well-established FTIR and Raman jet spectroscopic set-ups, the gas phase vibrational database of the cyclic formic acid dimer, (FF), has been reviewed and updated for the slow fingerprint vibrations [below 1500\,{\wn}] of the main and its three symmetrically deuterated isotopologues.\footnote{A. Nejad, K. A. E. Meyer, F. Kollipost, Z. Xue, M. A. Suhm , \textit{J. Chem. Phys.} \textbf{2021}, \textit{155}, 224301 and A. Nejad, PhD thesis, submitted (2022).} Experimental benchmarks validate the popular second-order vibrational perturbation theory approach in combination with high-level [hybrid] force fields which is shown to provide accurate predictions for moderate excitations of the intermolecular van der Waals\footnote{A. Nejad, M. A. Suhm , \textit{J. Indian Inst. Sci.} \textbf{2020}, \textit{100}, 5.} and intramolecular fingerprint vibrations$^\textit{a}$ of (FF). The new and extended benchmark-quality database of (FF) is particularly useful to guide recent efforts\footnote{C. Qu, J. M. Bowman, \textit{Phys. Chem. Chem. Phys.} \textbf{2019}, \textit{21}, 3397 and A. M. Santa Dar\'{i}a, G. Avila, E. M\'{a}tyus, \textit{Phys. Chem. Chem. Phys.} \textbf{2021}, \textit{23}, 6526.% } to accurately model the 24-dimensional vibrational dynamics of this prototypical model system in a `bottom-up' approach. As a byproduct, the number of assigned vibrational fundamentals [and selected overtone bands] of the vacuum-isolated formic acid trimer, F(FF), has been drastically increased.$^\textit{a}$ Since the polar dimer, FF, is a fragment of the trimer, the experimentally validated theoretical description of F(FF) promises to provide reliable spectral predictions for future gas phase spectroscopic searches of FF.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Genre of Resource

Conference Paper / Presentation

Language

eng

Handle URL

https://hdl.handle.net/2142/116845

DOI

https://doi.org/10.15278/isms.2022.RI02

Copyright and License Information

Copyright 2022 held by the authors

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