Work

Alchemical thermodynamic integration for ab initio free-energy calculations in solutions

Year: 2026

Type: preprint

Abstract: We develop an alchemical thermodynamic integration scheme that couples ab initio force calculators on the fly during Monte Carlo and molecular dynamics simulations. The implementation is validated against existing hybrid-Hamiltonian approaches. The scheme yields ab initio free energies of high-pressure Fe-Ni and ambient Li-Na liquid solutions that agree with previous calculations and reproduce the experimentally observed Li-Na miscibility gap. The code has an efficiency comparable to standard ab initio molecular dynamics. These results establish this scheme as a practical alchemical-integration framework for first-principles free-energy calculations in solutions.

Source: arXiv (Cornell University)

DOI: 10.48550/arxiv.2607.18750

Authors: Wei, Liangrui, Zhang, Feng, Wentzcovitch, Renata M., Ho, Kai-Ming, Sun, Yang

Institutions: Xiamen University, Iowa State University, Ames National Laboratory

Topic: Thermodynamic and Structural Properties of Metals and Alloys

Subfield: Mechanical Engineering

Field: Engineering

Domain: Physical Sciences

Open Access status: green

Funders: U.S. Department of Energy, Gordon and Betty Moore Foundation, Iowa State University, National Natural Science Foundation of China, Xiamen University, Office of Science, Basic Energy Sciences

Awards: G1212425923, G1286251239, G1418315740, G1519358529, G1866217153, G2316606464, G2327333655, G249831736, G285533474, G4381763660, G498139845, G524707868, G5959670421, G7004623220, Modeling Earth from the Atomic to Global Scale, G8943864594, G969889393

OpenAlex ID: W7170035181

Cites:

Cited by:

Related to: