10.57647/jtap.2026.2002.11

Study of Intra-Molecular C−H‧‧‧O Bonded Chair Conformer of (R)−(−)−Menthyl Acetate using Combined Spectroscopic and Computational Methods

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  • Kiran Gadivaddar1,
  • J. Tonannavar1,
  • Jayashree Tonannavar*1,
  1. Vibrational Spectroscopy Group/Molecular Modelling Laboratory, Department of Studies In Physics, Karnatak University, Dharwad – 580003, India

Received: 2025-08-16

Revised: 2025-09-20

Accepted: 2025-10-17

Published in Issue 2026-04-30

Published Online: 2026-02-05

Copyright (c) 2026 Kiran Gadivaddar, J. Tonannavar, Jayashree Tonannavar (Author)

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This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

1.
Gadivaddar K, Tonannavar J, Tonannavar J. Study of Intra-Molecular C−H‧‧‧O Bonded Chair Conformer of (R)−(−)−Menthyl Acetate using Combined Spectroscopic and Computational Methods. J Theor Appl phys. 2026 Apr. 30;20(2). Available from: https://oiccpress.com/jtap/article/view/18399
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Abstract

The intra-molecular C−H‧‧‧O bond has been studied in (R)−(−)−Menthyl Acetate employing both DFT and QT-AIM methods. The B3LYP/6−311+G(d,p) level has predicted a stable chair conformation in agreement with measured IR and Raman modes. This C−H‧‧‧O bonded chair conformer is also supported by a downfield shift at δ 4.68 ppm (computed δ 4.78 ppm) in the measured 1H NMR spectrum and positive values of electron density and its Laplacian obtained from QT−AIM. The computed H···O distance (2.351 Å) in C–H···O bond is shorter than the sum of van der Waals radii of H and O atoms, 2.720 Å. A strong positive Cotton effect at 232 nm in the ECD spectrum corresponds to the medium UV band at 241 nm (other bands: 219 and 276 nm) and is assigned to the n→π* transition. It is argued that the good agreement between computed CD band at 214 nm and its corresponding experimental band at 232 nm support proposed intra−molecular C−H‧‧‧O bonded chair conformer for (R)−(−)−Menthyl Acetate. The charge delocalization in C−H‧‧‧O bond is characterized by overlapping n(2)O→π*(C=O) natural bond orbitals with ~47 kcal/mol stabilization energy. The C−H‧‧‧O bonding and its neighbor atoms are shown in terms of electron localization function and localized orbital locator as electron density distributions and their spatial locations in the interaction.

Keywords

  • (R)−(−)−Menthyl Acetate,
  • NMR Spectrum,
  • ECD Spectrum,
  • DFT,
  • QT−AIM analysis,
  • ELF and LOL analyses
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