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  4. Hydrogen Diffusion and Trapping in α-Iron: The Role of Quantum and Anharmonic Fluctuations
 
research article

Hydrogen Diffusion and Trapping in α-Iron: The Role of Quantum and Anharmonic Fluctuations

Cheng, Bingqing  
•
Paxton, Anthony T.
•
Ceriotti, Michele  
2018
Physical Review Letters

We investigate the thermodynamics and kinetics of a hydrogen interstitial in magnetic α-iron, taking account of the quantum fluctuations of the proton as well as the anharmonicities of lattice vibrations and hydrogen hopping. We show that the diffusivity of hydrogen in the lattice of bcc iron deviates strongly from an Arrhenius behavior at and below room temperature. We compare a quantum transition state theory to explicit ring polymer molecular dynamics in the calculation of diffusivity. We then address the trapping of hydrogen by a vacancy as a prototype lattice defect. By a sequence of steps in a thought experiment, each involving a thermodynamic integration, we are able to separate out the binding free energy of a proton to a defect into harmonic and anharmonic, and classical and quantum contributions. We find that about 30% of a typical binding free energy of hydrogen to a lattice defect in iron is accounted for by finite temperature effects, and about half of these arise from quantum proton fluctuations. This has huge implications for the comparison between thermal desorption and permeation experiments and standard electronic structure theory. The implications are even greater for the interpretation of muon spin resonance experiments.

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Type
research article
DOI
10.1103/PhysRevLett.120.225901
Web of Science ID

WOS:000433915100015

Author(s)
Cheng, Bingqing  
Paxton, Anthony T.
Ceriotti, Michele  
Date Issued

2018

Published in
Physical Review Letters
Volume

120

Issue

22

Article Number

225901

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
FunderGrant Number

FNS

200021-159896 NQE

Available on Infoscience
October 31, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/162557
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