TY - JOUR

T1 - Unmasking quantum effects in the surface thermodynamics of fluid nanodrops

AU - Contreras, Sergio

AU - Martínez-Borquez, Alejandro

AU - Avendano, Carlos

AU - Gil-Villegas, Alejandro

AU - Jackson, George

PY - 2024/4/25

Y1 - 2024/4/25

N2 - The focus of our study is an in-depth investigation of the quantum effects associated with the surface tension and other thermodynamic properties of nanoscopic liquid drops. The behaviour of drops of quantum Lennard-Jones fluids is investigated with path-integral Monte Carlo simulations, and the test-area method is used to determine the surface tension of the spherical vapour-liquid interface. As the thermal de Broglie wavelength, λB, becomes more significant, the average density of the liquid drop decreases, with the drop becoming mechanically unstable at large wavelengths. As a consequence the surface tension is found to decrease monotonically with λB, vanishing altogether for dominant quantum interactions. Quantum effects can be significant leading to values which are notably lower than the classical thermodynamic limit, particularly for smaller drops. For planar interfaces (with infinite periodicity in the direction parallel to the interface), quantum effects are much less significant with the same values of λB, but are nevertheless consequential for values corresponding to hydrogen or helium-4 at the low temperatures of vapour-liquid coexistence. Large quantum effects are found for small drops of molecules with quantum interactions corresponding to water, ethane, methanol, and carbon dioxide, even at ambient conditions. The notable decrease in the density and tension has important consequences in reducing the Gibbs free-energy barrier of a nucleating cluster enhancing the nucleation kinetics of liquid drops and of bubble formation. This implies that drops would form at a much greater rate than is predicted by the classical nucleation theory.

AB - The focus of our study is an in-depth investigation of the quantum effects associated with the surface tension and other thermodynamic properties of nanoscopic liquid drops. The behaviour of drops of quantum Lennard-Jones fluids is investigated with path-integral Monte Carlo simulations, and the test-area method is used to determine the surface tension of the spherical vapour-liquid interface. As the thermal de Broglie wavelength, λB, becomes more significant, the average density of the liquid drop decreases, with the drop becoming mechanically unstable at large wavelengths. As a consequence the surface tension is found to decrease monotonically with λB, vanishing altogether for dominant quantum interactions. Quantum effects can be significant leading to values which are notably lower than the classical thermodynamic limit, particularly for smaller drops. For planar interfaces (with infinite periodicity in the direction parallel to the interface), quantum effects are much less significant with the same values of λB, but are nevertheless consequential for values corresponding to hydrogen or helium-4 at the low temperatures of vapour-liquid coexistence. Large quantum effects are found for small drops of molecules with quantum interactions corresponding to water, ethane, methanol, and carbon dioxide, even at ambient conditions. The notable decrease in the density and tension has important consequences in reducing the Gibbs free-energy barrier of a nucleating cluster enhancing the nucleation kinetics of liquid drops and of bubble formation. This implies that drops would form at a much greater rate than is predicted by the classical nucleation theory.

KW - Quantum drops

KW - Path-integral Monte Carlo

KW - Surface tension

KW - Test-area method

U2 - 10.1063/5.0196501

DO - 10.1063/5.0196501

M3 - Article

SN - 0021-9606

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

ER -