The pressure induced phase diagram of double-layer ice under confinement: a first-principles study

• Published in: Physical chemistry chemical physics : PCCP 2022-07, Vol.24 (27), p.16647-16654
• Main Authors: Jyothirmai, M. V, Abraham, B. Moses, Singh, Jayant K
• Format: Article
• Language: English
• Subjects: Bilayers; Bonding strength; Carbon nanotubes; Confinement; Density functional theory; Enthalpy; First principles; Hydrogen bonding; Phase diagrams; Phase transitions; Pressure
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d2cp01470j

Here, we present double-layer ice confined within various carbon nanotubes (CNTs) using state-of-the-art pressure induced (5 GPa to 5 GPa) dispersion corrected density functional theory (DFT) calculations. We find that the double-layer ice exhibits remarkably rich and diverse phase behaviors as a function of pressure with varying CNT diameters. The lattice cohesive energies for various pure double layer ice phases follow the order of hexagonal > pentagonal > square tube > hexagonal-close-packed (HCP) > square > buckled-rhombic (b-RH). The confinement width was found to play a crucial role in the square and square tube phases in the intermediate pressure range of about 01 GPa. Unlike the phase transition in pure bilayer ice structures, the relative enthalpies demonstrate that the pentagonal phase, rather than the hexagonal structure, is the most stable ice polymorph at ambient pressure as well as in a deep negative pressure region, whereas the b-RH phase dominates under high pressure. The relatively short OO distance of b-RH demonstrates the presence of a strong hydrogen bonding network, which is responsible for stabilizing the system. Here, we present double-layer ice confined within various carbon nanotubes (CNTs) using state-of-the-art pressure induced (5 GPa to 5 GPa) dispersion corrected density functional theory (DFT) calculations.