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Title: Energy benchmarks for water clusters and ice structures from an embedded many-body expansion

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4820906· OSTI ID:1565010
 [1];  [1];  [2];  [3];  [3]
  1. Univ. College London, Bloomsbury (United Kingdom)
  2. Univ. of Bristol (United Kingdom); Univ. of Southampton (United Kingdom)
  3. Univ. of Bristol (United Kingdom)
+ Show Author Affiliations

In this paper, we show how an embedded many-body expansion (EMBE) can be used to calculate accurate ab initio energies of water clusters and ice structures using wavefunction-based methods. We use the EMBE described recently by Bygrave et al. [J. Chem. Phys. 137, 164102 (2012)], in which the terms in the expansion are obtained from calculations on monomers, dimers, etc., acted on by an approximate representation of the embedding field due to all other molecules in the system, this field being a sum of Coulomb and exchange-repulsion fields. Our strategy is to separate the total energy of the system into Hartree-Fock and correlation parts, using the EMBE only for the correlation energy, with the Hartree-Fock energy calculated using standard molecular quantum chemistry for clusters and plane-wave methods for crystals. Our tests on a range of different water clusters up to the 16-mer show that for the second-order Møller-Plesset (MP2) method the EMBE truncated at 2-body level reproduces to better than 0.1 mEh/monomer the correlation energy from standard methods. The use of EMBE for computing coupled-cluster energies of clusters is also discussed. For the ice structures Ih, II, and VIII, we find that MP2 energies near the complete basis-set limit reproduce very well the experimental values of the absolute and relative binding energies, but that the use of coupled-cluster methods for many-body correlation (non-additive dispersion) is essential for a full description. Possible future applications of the EMBE approach are suggested.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
USDOE Office of Science (SC)
OSTI ID:
1565010
Journal Information:
Journal of Chemical Physics, Vol. 139, Issue 11; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 60 works
Citation information provided by
Web of Science

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Cited By (17)

Differential Many-Body Cooperativity in Electronic Spectra of Oligonuclear Transition-Metal Complexes journal October 2015
Recent advances in quantum‐mechanical molecular dynamics simulations of proton transfer mechanism in various water‐based environments journal May 2019
Competition of van der Waals and chemical forces on gold–sulfur surfaces and nanoparticles journal February 2017
FDE-vdW: A van der Waals inclusive subsystem density-functional theory journal July 2014
Benchmarking DFT and semiempirical methods on structures and lattice energies for ten ice polymorphs journal March 2015
Accelerating wavefunction in density-functional-theory embedding by truncating the active basis set journal July 2015
Probing the structural and dynamical properties of liquid water with models including non-local electron correlation journal August 2015
Perspective: How good is DFT for water? journal April 2016
B97-3c: A revised low-cost variant of the B97-D density functional method journal February 2018
Understanding non-covalent interactions in larger molecular complexes from first principles journal January 2019
CrystaLattE: Automated computation of lattice energies of organic crystals exploiting the many-body expansion to achieve dual-level parallelism journal October 2019
Fantasy versus reality in fragment-based quantum chemistry journal November 2019
The S66 Non-Covalent Interactions Benchmark Reconsidered Using Explicitly Correlated Methods Near the Basis Set Limit journal January 2018
Fast and accurate quantum Monte Carlo for molecular crystals journal February 2018
Discovering correlated fermions using quantum Monte Carlo journal August 2016
Probing the structural and dynamical properties of liquid water with models including non-local electron correlation text January 2015
FDE-vdW: A van der Waals Inclusive Subsystem Density-Functional Theory text January 2014

Figures / Tables (9)

FIG. 1(p. 5)figure FIG. 1
TABLE I(p. 5)table TABLE I
FIG. 2(p. 6)figure FIG. 2
TABLE II(p. 6)table TABLE II
FIG. 3(p. 7)figure FIG. 3
FIG. 4(p. 8)figure FIG. 4
TABLE III(p. 8)table TABLE III
FIG. 5(p. 10)figure FIG. 5
TABLE IV(p. 11)table TABLE IV

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