Medium-density amorphous ice unveils shear rate as a new dimension in water's phase diagram

• 成果类型: Article
• 署名作者: Ribeiro, Ingrid de Almeida; Dhabal, Debdas; Kumar, Rajat; Banik, Suvo; Sankaranarayanan, Subramanian K. R. S.; Molinero, Valeria
• 署名单位: Utah System of Higher Education; University of Utah; United States Department of Energy (DOE); Argonne National Laboratory; University of Illinois System; University of Illinois Chicago; University of Illinois Chicago Hospital; Indian Institute of Technology System (IIT System); Indian Institute of Technology (IIT) - Guwahati
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-12038
• DOI: 10.1073/pnas.2414444121
• 发表日期: 2024-11-26
• 关键词: energy; glassy; amorphization; DYNAMICS; liquid

摘要

Recent experiments revealed a new amorphous ice phase, medium-density amorphous ice (MDA), formed by ball-milling ice I-h at 77 K [Rosu-Finsen et al., Science 379, 474-478 (2023)]. MDA has density between that of low-density amorphous (LDA) and high-density amorphous (HDA) ices, adding to the complexity of water's phase diagram, known for its glass polyamorphism and two-state thermodynamics. The nature of MDA and its relation to other amorphous ices and liquid water remain unsolved. Here, we use molecular simulations under controlled pressure and shear rate at 77 K to produce and investigate MDA. We find that MDA formed at constant shear rate is a steady-state nonequilibrium shear-driven amorphous ice (SDA), that can be produced by shearing ice I-h, LDA, or HDA. Our results suggest that MDA could be obtained by ball-milling water glasses without crystallization interference. Increasing the shear rate at ambient pressure produces SDAs with densities ranging from LDA to HDA, revealing shear rate as a new thermodynamic variable in the nonequilibrium phase diagram of water. Indeed, shearing provides access to amorphous states inaccessible by controlling pressure and temperature alone. SDAs produced with shearing rates as high as 10(6) s(-1) sample the same region of the potential energy landscape than hyperquenched glasses with identical density, pressure, and temperature. Intriguingly, SDAs obtained by shearing at similar to 10(8) s(-1) have density, enthalpy, and structure indistinguishable from those of water instantaneously quenched from room temperature to 77 K over 10 ps, making them good approximants for the true glass of ambient liquid water.