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Free energy of crystal phases is commonly evaluated by thermodynamic integration (TDI) along a reversible path that involves an external potential. A persistent problem in this method is that a significant hysteresis is observed due to…

Materials Science · Physics 2010-02-27 Pankaj A. Apte

Steered molecular dynamics (SMD) simulations for the calculation of free energies are well suited for high-throughput molecular simulations on a distributed infrastructure due to the simplicity of the setup and parallel granularity of the…

Chemical Physics · Physics 2023-09-22 Toni Giorgino , Gianni De Fabritiis

Ultrafast, time-resolved spectroscopies enable the direct observation of non-equilibrium processes in condensed-phase systems and have revealed key insights into energy transport, hydrogen-bond dynamics, and vibrational coupling. While ab…

Chemical Physics · Physics 2025-09-01 Kit Joll , Philipp Schienbein

Path-integral molecular dynamics (PIMD) simulations are crucial for accurately capturing nuclear quantum effects in materials. However, their computational intensity and reliance on multiple software packages often limit their applicability…

We demonstrate an efficient and accurate, general-purpose first-principles blueprint for calculating anharmonic vibrational free energy and predicting structural phase transition temperatures of solids. Thermodynamic integration is…

Materials Science · Physics 2024-03-14 Junsoo Park , Zhigang Wu , John W. Lawson

We present a new method to evaluate vibrational free energies of atomic systems without a priori specification of an interatomic potential. Our model-agnostic approach leverages descriptors, high-dimensional feature vectors of atomic…

Materials Science · Physics 2025-03-05 Thomas D Swinburne , Clovis Lapointe , Mihai-Cosmin Marinica

A kink-based path integral method, previously applied to atomic systems, is modified and used to study molecular systems. The method allows the simultaneous evolution of atomic and electronic degrees of freedom. Results for CH$_4 $, NH$_3…

Chemical Physics · Physics 2009-11-11 Randall W. Hall

An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD) [J. Chem.…

Chemical Physics · Physics 2017-11-22 Xinzijian Liu , Jian Liu

The development and implementation of increasingly accurate methods for electronic structure calculations mean that, for many atomistic simulation problems, treating light nuclei as classical particles is now one of the most serious…

Materials Science · Physics 2016-02-12 Venkat Kapil , Joost VandeVondele , Michele Ceriotti

Calculating free energies is an important and notoriously difficult task for molecular simulations. The rapid increase in computational power has made it possible to probe increasingly complex systems, yet extracting accurate free energies…

Chemical Physics · Physics 2014-07-29 Viveca Lindahl , Jack Lidmar , Berk Hess

A method based on the Gibbs' adsorption isotherm is developed to calculate the decrease in interfacial free energy resulting from solute segregation at an internal interface, built on measured concentration profiles. Utilizing atom-probe…

Materials Science · Physics 2020-03-04 Ivan Blum , Sung-Il Baik , Mercouri G. Kanatzidis , David N. Seidman

We present a method for performing path integral molecular dynamics (PIMD) simulations for fermions and address its sign problem. PIMD simulations are widely used for studying many-body quantum systems at thermal equilibrium. However, they…

Chemical Physics · Physics 2020-05-07 Barak Hirshberg , Michele Invernizzi , Michele Parrinello

We push the boundaries of electronic structure-based \textit{ab-initio} molecular dynamics (AIMD) beyond 100 million atoms. This scale is otherwise barely reachable with classical force-field methods or novel neural network and machine…

Accurate free-energy calculations are essential for predicting thermodynamic properties and phase stability, but existing methods are limited: phonon-based approaches neglect anharmonicity and liquids, while molecular dynamics (MD) is…

Materials Science · Physics 2025-11-19 Ekaterina Spirande , Timofei Miryashkin , Andrei Kolmakov , Alexander Shapeev

Building on Paper I of this series, which introduced path integral Monte Carlo (PIMC) estimators for the derivative of the potential of mean force (PMF), we propose two path integral molecular dynamics (PIMD) integrators that can make use…

Chemical Physics · Physics 2021-10-08 Dmitri Iouchtchenko , Kevin P. Bishop , Pierre-Nicholas Roy

We present an accelerated ``on-the-fly'' coupled-cluster path-integral molecular dynamics (PIMD) method for finite-temperature simulations in which electron correlation and nuclear quantum effects are treated simultaneously. The approach is…

Chemical Physics · Physics 2026-05-20 Thomas Spura , Hossam Elgabarty , Thomas D. Kühne

Warm dense matter (WDM) is an active field of research, with applications ranging from astrophysics to inertial confinement fusion. Ionization degree and continuum lowering are important quantities to understand how materials behave under…

A new method ( PI-DFT ) which combines path integrals and density functional theory is proposed as a pathway to many fields of physics. Within path integral theory it is possible to construct particle densities without explicitly…

Condensed Matter · Physics 2007-05-23 Peter Borrmann

The introduction of machine learned potentials (MLPs) has greatly expanded the space available for studying Nuclear Quantum Effects computationally with ab initio path integral (PI) accuracy, with the MLPs' promise of an accuracy comparable…

Chemical Physics · Physics 2024-12-03 Bo Thomsen , Yuki Nagai , Keita Kobayashi , Ikutaro Hamada , Motoyuki Shiga

The accurate description of non-ideal quantum many-body systems is of prime importance for a host of applications within physics, quantum chemistry, material science, and related disciplines. At finite temperatures, the gold standard is…