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We perform path integral molecular dynamics (PIMD) simulations of a monatomic liquid that exhibits a liquid–liquid phase transition and liquid–liquid critical point. PIMD simulations are performed using different values of Planck’s constant h, allowing us to study the behavior of the liquid as nuclear quantum effects (NQE, i.e., atoms delocalization) are introduced, from the classical liquid ( h = 0) to increasingly quantum liquids ( h > 0). By combining the PIMD simulations with the ring-polymer molecular dynamics method, we also explore the dynamics of the classical and quantum liquids. We find that (i) the glass transition temperature of the low-density liquid (LDL) is anomalous, i.e., [Formula: see text] decreases upon compression. Instead, (ii) the glass transition temperature of the high-density liquid (HDL) is normal, i.e., [Formula: see text] increases upon compression. (iii) NQE shift both [Formula: see text] and [Formula: see text] toward lower temperatures, but NQE are more pronounced on HDL. We also study the glass behavior of the ring-polymer systems associated with the quantum liquids studied (via the path-integral formulation of statistical mechanics). There are two glass states in all the systems studied, low-density amorphous ice (LDA) and high-density amorphous ice (HDA), which are the glass counterparts of LDL and HDL. In all cases, the pressure-induced LDA–HDA transformation is sharp, reminiscent of a first-order phase transition. In the low-quantum regime, the LDA–HDA transformation is reversible, with identical LDA forms before compression and after decompression. However, in the high-quantum regime, the atoms become more delocalized in the final LDA than in the initial LDA, raising questions on the reversibility of the LDA–HDA transformation.
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Potential energy landscape formalism for quantum molecular liquids
Abstract The potential energy landscape (PEL) formalism is a powerful tool within statistical mechanics to study the thermodynamic properties of classical low-temperature liquids and glasses. Recently, the PEL formalism has been extended to liquids/glasses that obey quantum mechanics, but applications have been limited to atomistic model liquids. In this work, we extend the PEL formalism to liquid/glassy water using path-integral molecular dynamics (PIMD) simulations, where nuclear quantum effects (NQE) are included. Our PIMD simulations, based on the q-TIP4P/F water model, show that the PEL of quantum water is both Gaussian and anharmonic. Importantly, the ring-polymers associated to the O/H atoms in the PIMD simulations, collapse at the local minima of the PEL (inherent structures, IS) for both liquid and glassy states. This allows us to calculate, analytically, the IS vibrational density of states (IS-VDOS) of the ring-polymer system using the IS-VDOS of classical water (obtained from classical MD simulations). The role of NQE on the structural properties of liquid/glassy water at various pressures are discussed in detail. Overall, our results demonstrate that the PEL formalism can effectively describe the behavior of molecular liquids at low temperatures and in the glass states, regardless of whether the liquid/glass obeys classical or quantum mechanics.
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- PAR ID:
- 10592337
- Publisher / Repository:
- Comm. Chem.
- Date Published:
- Journal Name:
- Communications Chemistry
- Volume:
- 7
- Issue:
- 1
- ISSN:
- 2399-3669
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1038/s42004-024-01342-9
