Improved method of calculating ab initio high-temperature thermodynamic properties with application to ZrC
File(s)PhysRevB.91.214311.pdf (396.57 KB)
Published version
Author(s)
Type
Journal Article
Abstract
Thermodynamic properties of ZrC are calculated up to the melting point (
T
melt
≈
3700
K
), using density functional theory (DFT) to obtain the fully anharmonic vibrational contribution, and including electronic excitations. A significant improvement is found in comparison to results calculated within the quasiharmonic approximation. The calculated thermal expansion is in better agreement with experiment and the heat capacity reproduces rather closely a CALPHAD estimate. The calculations are presented as an application of a development of the upsampled thermodynamic integration using Langevin dynamics (UP-TILD) approach. This development, referred to here as two-stage upsampled thermodynamic integration using Langevin dynamics (TU-TILD), is the inclusion of tailored interatomic potentials to characterize an intermediate reference state of anharmonic vibrations on a two-stage path of thermodynamic integration between the original DFT quasiharmonic free energy and the fully anharmonic DFT free energy. This approach greatly accelerates the convergence of the calculation, giving a factor of improvement in efficiency of
∼
50
in the present case compared to the original UP-TILD approach, and it can be applied to a wide range of materials.
T
melt
≈
3700
K
), using density functional theory (DFT) to obtain the fully anharmonic vibrational contribution, and including electronic excitations. A significant improvement is found in comparison to results calculated within the quasiharmonic approximation. The calculated thermal expansion is in better agreement with experiment and the heat capacity reproduces rather closely a CALPHAD estimate. The calculations are presented as an application of a development of the upsampled thermodynamic integration using Langevin dynamics (UP-TILD) approach. This development, referred to here as two-stage upsampled thermodynamic integration using Langevin dynamics (TU-TILD), is the inclusion of tailored interatomic potentials to characterize an intermediate reference state of anharmonic vibrations on a two-stage path of thermodynamic integration between the original DFT quasiharmonic free energy and the fully anharmonic DFT free energy. This approach greatly accelerates the convergence of the calculation, giving a factor of improvement in efficiency of
∼
50
in the present case compared to the original UP-TILD approach, and it can be applied to a wide range of materials.
Date Issued
2015-06-30
Date Acceptance
2015-06-01
Citation
Physical review B: Condensed matter and materials physics, 2015, 91 (21)
ISSN
1098-0121
Publisher
American Physical Society
Journal / Book Title
Physical review B: Condensed matter and materials physics
Volume
91
Issue
21
Copyright Statement
© 2015 American Physical Society
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000357089800002&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
EP/F048084/1
EP/K01529X/1
J13614 (EP/K008749/1)
Subjects
Science & Technology
Physical Sciences
Physics, Condensed Matter
Physics
TOTAL-ENERGY CALCULATIONS
EMBEDDED-ATOM POTENTIALS
AUGMENTED-WAVE METHOD
MOLECULAR-DYNAMICS
ELASTIC PROPERTIES
BASIS-SET
METALS
1ST-PRINCIPLES
STABILITY
SILICON
Fluids & Plasmas
02 Physical Sciences
03 Chemical Sciences
Publication Status
Published