University of Illinois Urbana-Champaign

Theoretical And Experimental Rotational Spectroscopic Studies Of Substituted Benzoic Acid Heterodimers

Al-Jabiri, Mohamad H.

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https://hdl.handle.net/2142/116816

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Title
Theoretical And Experimental Rotational Spectroscopic Studies Of Substituted Benzoic Acid Heterodimers
Author(s)
Al-Jabiri, Mohamad H.
Contributor(s)
  • Jäger, Wolfgang
  • Cvitaš, Marko
  • Insausti, Aran
  • Eraković, Mihael
Issue Date
2022-06-21
Keyword(s)
Comparing theory and experiment
Abstract
The complex tunnelling dynamics of double proton transfer in carboxylic acid dimers has been the focus of many theoretical and experimental studies.$^{1,2}$ Here we combine spectroscopic and computational approaches to model and understand how functional groups in substituted benzoic acid heterodimers can influence these dynamics. Dimers of benzoic acid with its 4-chloro-, 4-nitro-, and 4-amino-analogues were studied using a 2 to 6 GHz chirped-pulse Fourier transform microwave spectrometer, which is based on the design by Pates et al.,$^{3}$ to obtain experimental tunneling line splittings. Jacobi field instanton theory (JFI)$^{4,5}$ was used to compute tunneling splittings in the ground vibrational state. The use of the JFI method, which necessitates a smaller number of potential energy and gradient calculations compared to other methods, enabled us to use ab initio on-the-fly potentials and compute the splitting in full dimensionality, in spite of the large system sizes. Furthermore, final expressions for the tunneling splittings provided a way to examine the influence of substituents on both the potential energy barrier height and shape, and on the vibrational modes, which can either promote or inhibit tunnelling. (1) Evangelisti, L.; Écija, P.; Cocinero, E. J.; Castaño, F.; Lesarri, A.; Caminati, W.; Meyer, R. J. Phys. Chem. Lett. 2012, 3 (24), 3770–3775. (2) Tautermann, C. S.; Voegele, A. F.; Liedl, K. R. J. Chem. Phys. 2004, 120 (2), 631–637. (3) Pérez, C.; Lobsiger, S.; Seifert, N. A.; Zaleski, D. P.; Temelso, B.; Shields, G. C.; Kisiel, Z.; Pate, B. H. Chem. Phys. Lett. 2013, 571, 1–15. (4) Eraković, M.; Vaillant, C. L.; Cvitaš, M. T. J. Chem. Phys. 2020, 152 (8), 084111. (5) Mil’nikov, G. V.; Nakamura, H. J. Chem. Phys. 2001, 115 (15), 6881–6897.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Handle URL
https://hdl.handle.net/2142/116816
DOI
https://doi.org/10.15278/isms.2022.TF11
Copyright and License Information
Copyright 2022 held by the authors

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Abstracts & Presentations - 2022 International Symposium on Molecular Spectroscopy PRIMARY