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Title: Fast and accurate quantum Monte Carlo for molecular crystals

Journal Article · · Proceedings of the National Academy of Sciences of the United States of America
 [1]; ORCiD logo [1];  [2];  [3];  [4];  [1]
  1. Univ. College London (United Kingdom). Dept. of Physics and Astronomy, Thomas Young Centre and London Centre for Nanotechnology
  2. Academy of Sciences of the Czech Republic, Prague (Czech Republic). J. Heyrovsky Inst. of Physical Chemistry; Charles Univ., Prague (Czech Republic). Dept. of Chemical Physics and Optics
  3. Univ. of Luxembourg (Luxembourg). Physics and Material Science Research Unit
  4. Univ. College London (United Kingdom). Thomas Young Centre and London Centre for Nanotechnology; Univ. College London (United Kingdom). Dept. of Earth Sciences
+ Show Author Affiliations

Computer simulation plays a central role in modern-day materials science. The utility of a given computational approach depends largely on the balance it provides between accuracy and computational cost. Molecular crystals are a class of materials of great technological importance which are challenging for even the most sophisticated ab initio electronic structure theories to accurately describe. This is partly because they are held together by a balance of weak intermolecular forces but also because the primitive cells of molecular crystals are often substantially larger than those of atomic solids. Here, we demonstrate that diffusion quantum Monte Carlo (DMC) delivers subchemical accuracy for a diverse set of molecular crystals at a surprisingly moderate computational cost. As such, we anticipate that DMC can play an important role in understanding and predicting the properties of a large number of molecular crystals, including those built from relatively large molecules which are far beyond reach of other high-accuracy methods.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC/ORNL, Oak Ridge, TN (Unted States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1565681
Journal Information:
Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 8 Vol. 115; ISSN 0027-8424
Publisher:
National Academy of SciencesCopyright Statement
Country of Publication:
United States
Language:
English

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Finite-size correction in many-body electronic structure calculations text January 2007
Smooth relativistic Hartree-Fock pseudopotentials for H to Ba and Lu to Hg text January 2009
Boosting the accuracy and speed of quantum Monte Carlo: size-consistency and time-step text January 2016
An efficient localized basis set for quantum Monte Carlo calculations on condensed matter text January 2004
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Parallel Nanoimprint Forming of One-Dimensional Chiral Semiconductor for Strain-Engineered Optical Properties journal August 2020
The potential of computed crystal energy landscapes to aid solid-form development journal June 2016
Predicting Molecular Crystal Properties from First Principles: Finite-Temperature Thermochemistry to NMR Crystallography journal October 2016
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Accurate first-principles structures and energies of diversely bonded systems from an efficient density functional journal June 2016
Accurate surface and adsorption energies from many-body perturbation theory journal July 2010
The high-throughput highway to computational materials design journal February 2013
The frontiers and the challenges journal March 2016
Facts and fictions about polymorphism journal January 2015
Practical quantum mechanics-based fragment methods for predicting molecular crystal properties journal January 2012
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy journal January 2014
Norm-conserving Hartree–Fock pseudopotentials and their asymptotic behavior journal January 2005
Smooth relativistic Hartree–Fock pseudopotentials for H to Ba and Lu to Hg journal May 2005
An efficient local coupled cluster method for accurate thermochemistry of large systems journal October 2011
Nonlocal pseudopotentials and diffusion Monte Carlo journal September 1991
A diffusion Monte Carlo algorithm with very small time‐step errors journal August 1993
Perspective on density functional theory journal April 2012
A benchmark for non-covalent interactions in solids journal August 2012
Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory journal September 2012
The embedded many-body expansion for energetics of molecular crystals journal October 2012
Pseudopotentials for correlated electron systems journal July 2013
Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals journal July 2013
Energy benchmarks for water clusters and ice structures from an embedded many-body expansion journal September 2013
Lattice energies of molecular solids from the random phase approximation with singles corrections journal September 2016
Revised M06-L functional for improved accuracy on chemical reaction barrier heights, noncovalent interactions, and solid-state physics journal July 2017
Chemical accuracy for the van der Waals density functional journal December 2009
Continuum variational and diffusion quantum Monte Carlo calculations journal December 2009
Quest for a universal density functional: the accuracy of density functionals across a broad spectrum of databases in chemistry and physics
  • Peverati, Roberto; Truhlar, Donald G.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011 https://doi.org/10.1098/rsta.2012.0476
journal March 2014
Finite-size effects and Coulomb interactions in quantum Monte Carlo calculations for homogeneous systems with periodic boundary conditions journal January 1996
Elimination of Coulomb finite-size effects in quantum many-body simulations journal February 1997
Finite-size errors in quantum many-body simulations of extended systems journal January 1999
Efficient localized basis set for quantum Monte Carlo calculations on condensed matter journal October 2004
Ab initio investigation of intermolecular interactions in solid benzene journal March 2008
Boosting the accuracy and speed of quantum Monte Carlo: Size consistency and time step journal June 2016
Twist-averaged boundary conditions in continuum quantum Monte Carlo algorithms journal June 2001
Finite-Size Correction in Many-Body Electronic Structure Calculations journal March 2008
Predicting Structure of Molecular Crystals from First Principles journal September 2008
Beyond the Random-Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations journal April 2011
Hydrogen Bonds and van der Waals Forces in Ice at Ambient and High Pressures journal October 2011
Strongly Constrained and Appropriately Normed Semilocal Density Functional journal July 2015
Finite-Size Error in Many-Body Simulations with Long-Range Interactions journal August 2006
Quantum Monte Carlo simulations of solids journal January 2001
Report on the sixth blind test of organic crystal structure prediction methods
  • Reilly, Anthony M.; Cooper, Richard I.; Adjiman, Claire S.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 4 https://doi.org/10.1107/S2052520616007447
journal August 2016
Insights into Current Limitations of Density Functional Theory journal August 2008
Ab initio determination of the crystalline benzene lattice energy to sub-kilojoule/mole accuracy journal August 2014
Density functional theory is straying from the path toward the exact functional journal January 2017
A conundrum for density functional theory journal January 2017
Finite-size correction in many-body electronic structure calculations text January 2007
Ab initio investigation of intermolecular interactions in solid benzene text January 2008
Chemical accuracy for the van der Waals density functional preprint January 2009
Beyond the Random Phase Approximation for the Electron Correlation Energy: The Importance of Single Excitations text January 2010
Perspective on density functional theory text January 2012
Pseudopotentials for correlated electron systems text January 2013
Strongly Constrained and Appropriately Normed Semilocal Density Functional preprint January 2015
An efficient localized basis set for quantum Monte Carlo calculations on condensed matter text January 2004
The Finite Size Error in Many-body Simulations with long-Ranged Interactions text January 2006
Finite size errors in quantum many-body simulations of extended systems text January 1998
An efficient local coupled cluster method for accurate thermochemistry of large systems text January 2011

Cited By (30)

Excited States with Selected Configuration Interaction-Quantum Monte Carlo: Chemically Accurate Excitation Energies and Geometries journal July 2019
Cost-Effective Quantum Mechanical Approach for Predicting Thermodynamic and Mechanical Stability of Pure-Silica Zeolites journal January 2019
Interactions between large molecules pose a puzzle for reference quantum mechanical methods journal June 2021
Understanding non-covalent interactions in larger molecular complexes from first principles journal January 2019
A complete description of thermodynamic stabilities of molecular crystals journal February 2022
Data-driven models of water and methane text January 2021
Accurate Predictions of Electron Binding Energies of Dipole-Bound Anions via Quantum Monte Carlo Methods text January 2018
On the physisorption of water on graphene: Sub-chemical accuracy from many-body electronic structure methods text January 2018
Excited states with selected CI-QMC: chemically accurate excitation energies and geometries text January 2019
An Assessment of Approximate Methods for Anharmonic Free Energies preprint January 2019
KITE: high-performance accurate modelling of electronic structure and response functions of large molecules, disordered crystals and heterostructures text January 2019
Random phase approximation with exchange for an accurate description of crystalline polymorphism text January 2021
Theory and practice of modeling van der Waals interactions in electronic-structure calculations journal January 2019
An efficient hybrid orbital representation for quantum Monte Carlo calculations journal August 2018
Understanding non-covalent interactions in larger molecular complexes from first principles journal January 2019
A new scheme for fixed node diffusion quantum Monte Carlo with pseudopotentials: Improving reproducibility and reducing the trial-wave-function bias journal October 2019
Interaction between water and carbon nanostructures: How good are current density functional approximations? journal October 2019
Efficient and accurate description of adsorption in zeolites journal December 2019
Variational and diffusion quantum Monte Carlo calculations with the CASINO code journal April 2020
The quantum nature of hydrogen journal January 2019
QMCPACK : an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids journal April 2018
Simplified DFT methods for consistent structures and energies of large systems journal May 2018
KITE: high-performance accurate modelling of electronic structure and response functions of large molecules, disordered crystals and heterostructures journal February 2020
Efficient method for grand-canonical twist averaging in quantum Monte Carlo calculations journal December 2019
Quantum Monte Carlo calculations of van der Waals interactions between aromatic benzene rings journal May 2018
QMCPACK : An open source ab initio Quantum Monte Carlo package for the electronic structure of atoms, molecules, and solids text January 2018
An efficient hybrid orbital representation for quantum Monte Carlo calculations text January 2018
The quantum nature of hydrogen preprint January 2018
Interaction between water and carbon nanostructures: How good are current density functional approximations? preprint January 2019
Variational and Diffusion Quantum Monte Carlo Calculations with the CASINO Code text January 2020

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