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Free energy evaluation in molecular simulations of both classical and quantum systems is computationally intensive and requires sophisticated algorithms. This is because free energy depends on the volume of accessible phase space, a quantity that is inextricably linked to the integration measure in a coordinate representation of a many-body problem. In contrast, the same problem expressed as a field theory (auxiliary field or coherent states) isolates the particle number as a simple parameter in the Hamiltonian or action functional and enables the identification of a chemical potential field operator. We show that this feature leads a “direct” method of free energy evaluation, in which a particle model is converted to a field theory and appropriate field operators are averaged using a field-theoretic simulation conducted with complex Langevin sampling. These averages provide an immediate estimate of the Helmholtz free energy in the canonical ensemble and the entropy in the microcanonical ensemble. The method is illustrated for a classical polymer solution, a block copolymer melt exhibiting liquid crystalline and solid mesophases, and a quantum fluid of interacting bosons.
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Preserving positivity in density-explicit field-theoretic simulations
Field-theoretic simulations are numerical methods for polymer field theory, which include fluctuation corrections beyond the mean-field level, successfully capturing various mesoscopic phenomena. Most field-theoretic simulations of polymeric fluids use the auxiliary field (AF) theory framework, which employs Hubbard–Stratonovich transformations for the particle-to-field conversion. Nonetheless, the Hubbard–Stratonovich transformation imposes significant limitations on the functional form of the non-bonded potentials. Removing this restriction on the non-bonded potentials will enable studies of a wide range of systems that require multi-body or more complex potentials. An alternative representation is the hybrid density-explicit auxiliary field theory (DE-AF), which retains both a density field and a conjugate auxiliary field for each species. While the DE-AF representation is not new, density-explicit field-theoretic simulations have yet to be developed. A major challenge is preserving the real and non-negative nature of the density field during stochastic evolution. To address this, we introduce positivity-preserving schemes that enable the first stable and efficient density-explicit field-theoretic simulations (DE-AF FTS). By applying the new method to a simple fluid, we find thermodynamically correct results at high densities, but the algorithm fails in the dilute regime. Nonetheless, DE-AF FTS is shown to be broadly applicable to dense fluid systems including a simple fluid with a three-body non-bonded potential, a homopolymer solution, and a diblock copolymer melt.
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- Award ID(s):
- 2104255
- PAR ID:
- 10633198
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 161
- Issue:
- 24
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0241609
