The Formic Acid Monomer: Extension Of The Vibrational Database And Rigorous Electronic And Nuclear Vibrational Structure Benchmarks

Nejad, Arman

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https://hdl.handle.net/2142/116856 Copy

Description

Title

The Formic Acid Monomer: Extension Of The Vibrational Database And Rigorous Electronic And Nuclear Vibrational Structure Benchmarks

Author(s)

Nejad, Arman

Contributor(s)

• Suhm, Martin A.
• Sibert, Edwin

Issue Date

2022-06-21

Keyword(s)

Mini-symposium: Benchmarking in Spectroscopy

Abstract

\begin{wrapfigure}{r}{0pt} \includegraphics[scale=0.75]{1.eps} \end{wrapfigure} The vibrational spectroscopy of formic acid, F, has seen new and important experimental and theoretical impulses in the past six years.\footnote{% (exp) K. Hull, T. Wells, B. E. Billinghurst, H. Bunn, P. L. Raston, \textit{AIP Adv.} \textbf{2019}, \textit{9}, 015021; K. A. E. Meyer, M. A. Suhm, \textit{Chem. Sci.} \textbf{2019}, \textit{10}, 6285; A. Nejad, M. A. Suhm, K. A. E. Meyer, \textit{Phys. Chem. Chem. Phys.} \textbf{2020}, \textit{22}, 25492. (theo) D. P. Tew, W. Mizukami, \textit{J. Phys. Chem. A} \textbf{2016}, \textit{120}, 9815; F. Richter, P. Carbonni\`{e}re, \textit{J. Chem. Phys.} \textbf{2018}, \textit{148}, 064303; A. Aerts, P. Carbonni\`{e}re, F. Richter, A. Brown, \textit{J. Chem. Phys.} \textbf{2020}, \textit{152}, 024305; A. Nejad, E. L. Sibert III, \textit{J. Chem. Phys.} \textbf{2021}, \textit{154}, 064301.% } In a combined experimental and theoretical approach, the vibrational database of F below 4000\,{\wn} is reviewed and extended to 189 band centres [$\sim$300\% increase], including a plethora of highly-excited vibrational states, both torsional conformers, and several isotopologues [$^1$H, $^2$H, $^{12}$C, $^{13}$C, and $^{16}$O].\footnote{% A. Nejad, PhD thesis, submitted (2022).% } Essentially, the vibrational characterisation of its skeletal modes below 3500\,{\wn} can be regarded as complete which is also an important stepping stone in understanding the complex vibrational dynamics of its cyclic dimer.\footnote{A. Nejad, K. A. E. Meyer, F. Kollipost, Z. Xue, M. A. Suhm , \textit{J. Chem. Phys.} \textbf{2021}, \textit{155}, 224301% } A new key insight is that the impact of the OH bend-torsion resonance [\nub{5} and 2\nub{9}] on the entire vibrational dynamics of \textit{trans}-HCOOH is more far-reaching than previously believed. Beyond 3500\,{\wn}, which is also near the expected \textit{trans}${\rightarrow}$\textit{cis} isomerisation threshold, this resonance polyad is indicated to play an important role in the perturbations of the OH stretching fundamental [\nub{1}]. In this contribution, new spectroscopic developments are summarised and promising future research directions for F are discussed. In particular, its importance and suitability for the purpose of benchmarking electronic and nuclear vibrational methodologies are highlighted.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Handle URL

https://hdl.handle.net/2142/116856

DOI

https://doi.org/10.15278/isms.2022.TI09

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Copyright 2022 held by the authors

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