First Principles Predictions of Van der Waals Bonded Inorganic Crystal Structures: Test Case, HgCl2

Valentino R. Cooper; Kelling J. Donald

doi:10.1016/j.phpro.2015.07.104

First Principles Predictions of Van der Waals Bonded Inorganic Crystal Structures: Test Case, HgCl₂

Valentino R. Cooper, Kelling J. Donald

Materials Science and Technology Div

Research output: Contribution to journal › Conference article › peer-review

3 Scopus citations

Abstract

We study the crystals structure and stability of four possible polymorphs of HgCl₂ using first principles density functional theory. Mercury (II) halides are a unique class of materials which, depending on the halide species, form in a wide range of crystal structures, ranging from densely packed solids to layered materials and molecular solids. Predicting the groundstate structure of any member of this group from first principles, therefore, requires a general purpose functional that treats van der Waals bonding and covalent/ionic bonding adequately. Here, we demonstrate that the non-local van der Waals density functional paired with the C09 exchange functional meets this bar for HgCl₂. In particular, this functional is able to predict the correct groundstate among the structures tested as well as having extremely good agreement with the experimentally known crystal structure. These results highlight the maturity of this functional and open the door to using this method for truly first principles crystal structure predictions.

Original language	English
Pages (from-to)	25-31
Number of pages	7
Journal	Physics Procedia
Volume	68
DOIs	https://doi.org/10.1016/j.phpro.2015.07.104
State	Published - 2015
Event	28th Workshop on Computer Simulation Studies in Condensed Matter Physics, CSP 2015 - Athens, United States Duration: Feb 23 2015 → Feb 27 2015

Funding

K.D. acknowledges support through the HERE program at ORNL. V.R.C. was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Sciences and Engineering and used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Division of Materials Sciences and Engineering

Keywords

London dispersion
crystal structure prediction
density functional theory
van der Waals
vdW-DF

Access to Document

10.1016/j.phpro.2015.07.104

Cite this

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title = "First Principles Predictions of Van der Waals Bonded Inorganic Crystal Structures: Test Case, HgCl2",

abstract = "We study the crystals structure and stability of four possible polymorphs of HgCl2 using first principles density functional theory. Mercury (II) halides are a unique class of materials which, depending on the halide species, form in a wide range of crystal structures, ranging from densely packed solids to layered materials and molecular solids. Predicting the groundstate structure of any member of this group from first principles, therefore, requires a general purpose functional that treats van der Waals bonding and covalent/ionic bonding adequately. Here, we demonstrate that the non-local van der Waals density functional paired with the C09 exchange functional meets this bar for HgCl2. In particular, this functional is able to predict the correct groundstate among the structures tested as well as having extremely good agreement with the experimentally known crystal structure. These results highlight the maturity of this functional and open the door to using this method for truly first principles crystal structure predictions.",

keywords = "London dispersion, crystal structure prediction, density functional theory, van der Waals, vdW-DF",

author = "Cooper, {Valentino R.} and Donald, {Kelling J.}",

note = "Publisher Copyright: {\textcopyright} 2015 The Authors. Published by Elsevier B.V.; 28th Workshop on Computer Simulation Studies in Condensed Matter Physics, CSP 2015 ; Conference date: 23-02-2015 Through 27-02-2015",

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T1 - First Principles Predictions of Van der Waals Bonded Inorganic Crystal Structures

T2 - 28th Workshop on Computer Simulation Studies in Condensed Matter Physics, CSP 2015

AU - Cooper, Valentino R.

AU - Donald, Kelling J.

PY - 2015

Y1 - 2015

N2 - We study the crystals structure and stability of four possible polymorphs of HgCl2 using first principles density functional theory. Mercury (II) halides are a unique class of materials which, depending on the halide species, form in a wide range of crystal structures, ranging from densely packed solids to layered materials and molecular solids. Predicting the groundstate structure of any member of this group from first principles, therefore, requires a general purpose functional that treats van der Waals bonding and covalent/ionic bonding adequately. Here, we demonstrate that the non-local van der Waals density functional paired with the C09 exchange functional meets this bar for HgCl2. In particular, this functional is able to predict the correct groundstate among the structures tested as well as having extremely good agreement with the experimentally known crystal structure. These results highlight the maturity of this functional and open the door to using this method for truly first principles crystal structure predictions.

AB - We study the crystals structure and stability of four possible polymorphs of HgCl2 using first principles density functional theory. Mercury (II) halides are a unique class of materials which, depending on the halide species, form in a wide range of crystal structures, ranging from densely packed solids to layered materials and molecular solids. Predicting the groundstate structure of any member of this group from first principles, therefore, requires a general purpose functional that treats van der Waals bonding and covalent/ionic bonding adequately. Here, we demonstrate that the non-local van der Waals density functional paired with the C09 exchange functional meets this bar for HgCl2. In particular, this functional is able to predict the correct groundstate among the structures tested as well as having extremely good agreement with the experimentally known crystal structure. These results highlight the maturity of this functional and open the door to using this method for truly first principles crystal structure predictions.

KW - London dispersion

KW - crystal structure prediction

KW - density functional theory

KW - van der Waals

KW - vdW-DF

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