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Nuclear Quantum Effects in Hydroxide Hydrate Along the H-Bond Bifurcation Pathway

Arandhara, M and Ramesh, SG (2024) Nuclear Quantum Effects in Hydroxide Hydrate Along the H-Bond Bifurcation Pathway. In: Journal of Physical Chemistry A, 128 (9). pp. 1600-1610.

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Official URL: https://doi.org/10.1021/acs.jpca.3c08027


Path integral (PI) simulations are used to explore nuclear quantum effects (NQEs) in hydroxide hydrate and its perdeuterated isotopomer along the H-bond bifurcation pathway. Toward this, a new potential energy surface using the symmetric gradient domain machine learning method with ab initio data at the CCSD(T)/aug-cc-pVTZ level is built. From PI umbrella sampling (US) simulations, free energy profiles along the bifurcation coordinate are explored as a function of temperature. At ambient temperature, the bifurcation barrier is increased upon inclusion of NQEs. At low temperatures in the deep tunneling regime, the barrier is strongly decreased and flattened. These trends are examined, and the role of the O-O distance is also investigated through two-dimensional US simulations. © 2024 American Chemical Society.

Item Type: Journal Article
Publication: Journal of Physical Chemistry A
Publisher: American Chemical Society
Additional Information: The copyright for this article belongs to American Chemical Society.
Keywords: Bifurcation (mathematics); Free energy; Hydrates; Learning systems; Potential energy; Quantum chemistry, Gradient domain; H-bonds; Hydroxide hydrates; Isotopomers; Nuclear quantum effects; Path-integral simulation; Potential-energy surfaces; Sampling simulation; Symmetrics; Umbrella sampling, Hydration, hydroxide, ab initio calculation; article; controlled study; environmental temperature; human; low temperature; machine learning; major clinical study; signal transduction; simulation; temperature
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 16 May 2024 05:41
Last Modified: 16 May 2024 05:41
URI: https://eprints.iisc.ac.in/id/eprint/84519

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