Direct Elucidation Of The Reason For Almost The Same Bond Lengths For The C-h And C-d Bonds In C6h6 And C6d6: A Path Integral Molecular Dynamics Study

Udagawa, Taro

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https://hdl.handle.net/2142/116763 Copy

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Title

Direct Elucidation Of The Reason For Almost The Same Bond Lengths For The C-h And C-d Bonds In C6h6 And C6d6: A Path Integral Molecular Dynamics Study

Author(s)

Udagawa, Taro

Contributor(s)

• Tachikawa, Masanori
• Nagashima, Umpei
• Hirano, Tsuneo
• Baba, Masaaki
• Kuwahata, Kazuaki
• Tanaka, Hikaru

Issue Date

2022-06-20

Keyword(s)

Comparing theory and experiment

Abstract

Recently, Baba group found that ro-vibrationally averaged bond lengths of C--H and C--D are observed as being almost identical ($r_{\rm 0,eff}$(C--H) $\cong$ $r_{\rm 0,eff}$(C--D)) for planar aromatic hydrocarbons from high-resolution laser spectroscopy.\footnote{S. Kunishige, T. Katori, M. Baba, et al., J. Chem. Phys. {\bf 143}, 244302 (2015).} Quite recently, the reason of the same $r_{\rm 0,eff}$(C--H) and $r_{\rm 0,eff}$(C--D) bond lengths has been brilliantly unveiled by Hirano et al. by high-level \textit{ab initio} molecular orbital calculations.\footnote{T. Hirano, U. Nagashima, M. Baba, J. Mol. Struct. {\bf 1243}, 130537 (2021).} They revealed that the experimental bond lengths derived from effective rotational constants are "not" the ro-vibrationally averaged bond lengths but their projected lengths on the principle axis. In this study, we have carried out the path integral molecular dynamics (PIMD) simulations for ${\rm C_6H_6}$ and ${\rm C_6D_6}$ to directly estimate the distribution of the C--H and C--D bond lengths projected onto the principle axis. Our PIMD simulation strongly supports the previous explanation by Hirano et al.$^{a}$ for the experimentally observed fact ($r_{\rm 0,eff}$(C--H) $\cong$ $r_{\rm 0,eff}$(C--D)) in ${\rm C_6H_6}$ and ${\rm C_6D_6}$.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Handle URL

https://hdl.handle.net/2142/116763

DOI

https://doi.org/10.15278/isms.2022.MJ07

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