# An efficient approach to ab initio Monte Carlo simulation.

@article{Leiding2013AnEA, title={An efficient approach to ab initio Monte Carlo simulation.}, author={Jeffery Allen Leiding and Joshua D. Coe}, journal={The Journal of chemical physics}, year={2013}, volume={140 3}, pages={ 034106 } }

We present a Nested Markov chain Monte Carlo (NMC) scheme for building equilibrium averages based on accurate potentials such as density functional theory. Metropolis sampling of a reference system, defined by an inexpensive but approximate potential, was used to substantially decorrelate configurations at which the potential of interest was evaluated, thereby dramatically reducing the number needed to build ensemble averages at a given level of precision. The efficiency of this procedure was…

## 8 Citations

### Accelerating ab Initio Simulation via Nested Monte Carlo and Machine Learned Reference Potentials.

- ChemistryThe journal of physical chemistry. B
- 2020

This paper shows that AIMC can be brought up to, and even above, the performance levels of AIMD via a hybrid nested sampling / machine learning (ML) strategy, and shows that high performance and exact sampling at the desired level of theory can be realized even when the trained interaction has appreciable differences from the ab initio potential.

### Reactive Monte Carlo sampling with an ab initio potential.

- ChemistryThe Journal of chemical physics
- 2016

The first application of reactive Monte Carlo in a first-principles context is presented, finding that there are regions of state space for which RxMC sampling is much more efficient than AIMD due to the "rare-event" character of chemical reactions.

### Layered nested Markov chain Monte Carlo.

- Computer ScienceThe Journal of chemical physics
- 2018

It is shown that L-NMCMC, when combined with a free-energy perturbation formalism, provides a straightforward means to construct approximate free- energy surfaces at no additional computational cost using the sampling distributions of each auxiliary Markov chain.

### First principles reactive simulation for equation of state prediction.

- ChemistryThe Journal of chemical physics
- 2021

It is found that DFT predicts the energy of PETN detonation products to be systematically too high relative to the unreacted neat crystalline material, resulting in an underprediction of the detonation velocity, pressure, and temperature at the Chapman-Jouguet state.

### Generation of Quantum Configurational Ensembles Using Approximate Potentials.

- ChemistryJournal of chemical theory and computation
- 2021

It is shown that FF reparametrization is an efficient route to generate FFs that reproduce QM results more closely, which, in turn, can be used as low-cost models to achieve the gold standard QM accuracy.

### First-Principles Simulations of CuCl in High-Temperature Water Vapor.

- PhysicsThe journal of physical chemistry. B
- 2021

Molecular dynamics is not the most appropriate technique for studying aggregation in vapor phases, even at relatively high temperatures, and first-principles Monte Carlo and molecular dynamics simulations exploring hydrated clusters of the form CuCl(H2O)n find that the average hydration number substantially increases with increasing density.

### Modelling of framework materials at multiple scales: current practices and open questions

- Materials SciencePhilosophical Transactions of the Royal Society A
- 2019

A short highlight of the current state of methodologies for modelling framework materials at multiple scales is proposed, putting together a brief review of new methods and recent endeavours, as well as outlining some of the open challenges in this field.

### Direct coupling of first-principles calculations with replica exchange Monte Carlo sampling of ion disorder in solids

- Materials ScienceJournal of physics. Condensed matter : an Institute of Physics journal
- 2019

The possibility of bypassing fitting models will lead to investigation of disordered systems where cluster expansion is known to perform badly, for example, systems with large lattice deformation due to defects, or systems where long-range interactions dominate such as electrochemical interfaces.

## References

SHOWING 1-10 OF 95 REFERENCES

### Toward a Monte Carlo program for simulating vapor-liquid phase equilibria from first principles

- ChemistryComput. Phys. Commun.
- 2005

### Nested Markov chain Monte Carlo sampling of a density functional theory potential: equilibrium thermodynamics of dense fluid nitrogen.

- ChemistryThe Journal of chemical physics
- 2009

An optimized variant of the nested Markov chain Monte Carlo method is applied to fluid N(2), isothermal-isobaric (NPT) ensemble sampling on the basis of a pair potential (the "reference" system) is used to enhance the efficiency of sampling based on Perdew-Burke-Ernzerhof density functional theory.

### Using a classical potential as an efficient importance function for sampling from an ab initio potential

- Chemistry, Physics
- 2000

In this paper the ab initio potential of mean force for the formic acid–water system is calculated in a Monte Carlo simulation using a classical fluctuating charge molecular mechanics potential to…

### Ab initio Monte Carlo simulations applied to a Si 5 cluster

- Physics
- 2007

An ab initio Monte Carlo (MC) program has been developed, where the total configurational energies at each MC step are obtained via density functional theory using localized numerical orbitals as…

### Efficient sampling for ab initio Monte Carlo simulation of molecular clusters using an interpolated potential energy surface.

- ChemistryThe Journal of chemical physics
- 2009

An approach is developed to enhance sampling for ab initio Monte Carlo and ab initio path integral Monte Carlo calculations of molecular clusters by utilizing an approximate potential as a guide to…

### Density functional theory guided Monte Carlo simulations: application to melting of Na13.

- PhysicsThe Journal of chemical physics
- 2012

A density functional theory (DFT) based Monte Carlo simulation method in which a simple energy function gets fitted on-the-fly to DFT energies and gradients, which effectively breaks down the problem of fitting the entire potential energy surface (PES) into many easier problems, which are to fit small local regions of the PES.

### Ab initio Monte Carlo simulation using multicanonical algorithm: temperature dependence of the average structure of water dimer

- Chemistry
- 1999

A multicanonical Monte Carlo simulation has been performed to investigate average structural changes in the water dimer with temperature. Potential energy was calculated by the ab initio MO method at…

### Monte Carlo simulations using sampling from an approximate potential

- Computer Science
- 2003

A simulation algorithm is proposed in which the potential energy function used in a Monte Carlo simulation is replaced with one that is less expensive to evaluate, coupled with a correction step…

### Isobaric-isothermal monte carlo simulations from first principles: application to liquid water at ambient conditions.

- Environmental ScienceChemphyschem : a European journal of chemical physics and physical chemistry
- 2005

The fluctuations in the system volume encountered in simulations in the isobaric-isothermal ensemble require a reconsideration of the suitability of the typical charge-density cutoff and the regular grid-generation method previously used for the computation of the electrostatic energy in first-principles simulations inThe microcanonical or canonical ensembles.