High-temperature effects for transition state calculations in solids

Ke, Chengxuan1; Nie, Chenxi1; Luo, Guangfu1,2

2023-11-28

10.1063/5.0153258

JOURNAL OF CHEMICAL PHYSICS   影响因子和分区

0021-9606

1089-7690

Transition state calculation is a critical technique to understand and predict versatile dynamical phenomena in solids. However, the transition state results obtained at 0 K are often utilized for the prediction or interpretation of dynamical processes at high temperatures, and the error bars of such an approximation are largely unknown. In this benchmark study, all the major temperature effects, including lattice expansion, lattice vibration, electron excitation, and band-edge shift, are evaluated with first-principles calculations for defect diffusion in solids. With the inclusion of these temperature effects, the notable discrepancies between theoretical predictions at 0 K and the experimental diffusivities at high temperatures are dramatically reduced. In particular, we find that lattice expansion and lattice vibration are the dominant factors lowering the defect formation energies and hopping barriers at high temperatures, but the electron excitation exhibits minor effects. In sharp contrast to typical assumptions, the attempt frequency with lattice expansion and vibration varies significantly with materials: several THz for aluminum bulk but surprisingly over 500 THz for 4H-SiC. For defects in semiconductors, the band-edge shift is also significant at high temperatures and plays a vital role in defect diffusion. We expect that this study would help accurately predict the dynamical processes at high temperatures.

SCI ; EI

英语

第一 ; 通讯

Guangdong Provincial Key Laboratory of Computational Science and Material Designhttps://doi.org/10.13039/501100020745[2019B030301001] ; Guangdong Provincial Key Laboratory of Computational Science and Material Design[2017ZT07C062] ; Introduced Innovative R&D Team of Guangdong[52273226] ; National Foundation of Natural Science, China[JCYJ20200109141412308]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:001109960700013

AIP Publishing

20234915143267

Defects ; Lattice vibrations ; Silicon carbide ; Temperature ; Thermal expansion ; Wide band gap semiconductors

Thermodynamics:641.1 ; Semiconducting Materials:712.1 ; Inorganic Compounds:804.2 ; Crystal Lattice:933.1.1 ; Materials Science:951

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Computat Sci & Mat Design, Shenzhen 518055, Peoples R China

Ke, Chengxuan,Nie, Chenxi,Luo, Guangfu. High-temperature effects for transition state calculations in solids[J]. JOURNAL OF CHEMICAL PHYSICS,2023,159(20).

Ke, Chengxuan,Nie, Chenxi,&Luo, Guangfu.(2023).High-temperature effects for transition state calculations in solids.JOURNAL OF CHEMICAL PHYSICS,159(20).

Ke, Chengxuan,et al."High-temperature effects for transition state calculations in solids".JOURNAL OF CHEMICAL PHYSICS 159.20(2023).