Nuclear quantum effects in gas-phase ethylene glycol

Arandhara, M and Ramesh, SG (2024) Nuclear quantum effects in gas-phase ethylene glycol. In: Physical Chemistry Chemical Physics, 26 (28). pp. 19529-19542.

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Abstract

Path integral molecular simulations are used to explore the nuclear quantum effects (NQEs) on the structure, dihedral landscape and infrared spectrum of ethylene glycol. The simulations are carried out on a new reaction surface Hamiltonian-based model potential energy surface, with special focus on the role of the OCCO and HOCC dihedrals. In contrast with classical simulations, we analyse how the intramolecular interactions between the OH groups change due to zero-point effects as well as temperature. These are found to be weak. The NQEs on the free energy profile along the OCCO dihedral are analysed, where notable effects are seen at low temperatures and found to be correlated with the radii of gyration of the atoms. Finally, the power spectrum of the molecule from path integral simulations is compared with the experimental infrared spectrum, yielding a good agreement of band positions. © 2024 The Royal Society of Chemistry.

Item Type:	Journal Article
Publication:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
Additional Information:	The copyright for this article belongs to Royal Society of Chemistry.
Keywords:	Ethylene; Free energy; Polyols; Potential energy; Quantum chemistry; Quantum theory; Surface reactions, Classical simulation; Gas-phases; Infrared spectrum; Intramolecular interactions; Model potential; Molecular simulations; Nuclear quantum effects; Path integral; Potential-energy surfaces; Reaction surfaces, Ethylene glycol
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	19 Dec 2024 04:27
Last Modified:	19 Dec 2024 04:27
URI:	http://eprints.iisc.ac.in/id/eprint/85892

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