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 Copy

Description

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

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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