Issue 19, 2020

Quantum kinetic energy and isotope fractionation in aqueous ionic solutions

Abstract

At room temperature, the quantum contribution to the kinetic energy of a water molecule exceeds the classical contribution by an order of magnitude. The quantum kinetic energy (QKE) of a water molecule is modulated by its local chemical environment and leads to uneven partitioning of isotopes between different phases in thermal equilibrium, which would not occur if the nuclei behaved classically. In this work, we use ab initio path integral simulations to show that QKEs of the water molecules and the equilibrium isotope fractionation ratios of the oxygen and hydrogen isotopes are sensitive probes of the hydrogen bonding structures in aqueous ionic solutions. In particular, we demonstrate how the QKE of water molecules in path integral simulations can be decomposed into translational, rotational and vibrational degrees of freedom, and use them to determine the impact of solvation on different molecular motions. By analyzing the QKEs and isotope fractionation ratios, we show how the addition of the Na+, Cl and HPO42− ions perturbs the competition between quantum effects in liquid water and impacts their local solvation structures.

Graphical abstract: Quantum kinetic energy and isotope fractionation in aqueous ionic solutions

Article information

Article type
Paper
Submitted
02 ربيع الثاني 1441
Accepted
13 جمادى الأولى 1441
First published
13 جمادى الأولى 1441

Phys. Chem. Chem. Phys., 2020,22, 10490-10499

Author version available

Quantum kinetic energy and isotope fractionation in aqueous ionic solutions

L. Wang, M. Ceriotti and T. E. Markland, Phys. Chem. Chem. Phys., 2020, 22, 10490 DOI: 10.1039/C9CP06483D

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