While the accurate description of redox reactions remains a challenge for first-principles calculations,it has been shown that extended Hubbard functionals(DFT+U+V)can provide a reliable approach,mitigating self-inter...While the accurate description of redox reactions remains a challenge for first-principles calculations,it has been shown that extended Hubbard functionals(DFT+U+V)can provide a reliable approach,mitigating self-interaction errors,in materials with strongly localized d or f electrons.Here,we first show that DFT+U+V molecular dynamics is capable of following the adiabatic evolution of oxidation states over time,using representative Li-ion cathode materials.In turn,this allows to develop redoxaware machine-learning potentials.Weshowthat considering atoms with different oxidation states(as accurately predicted by DFT+U+V)as distinct species in the training leads to potentials that are able to identify the correct ground state and pattern of oxidation states for redox elements present.This can be achieved,e.g.,through a systematic combinatorial search for the lowest-energy configuration or with stochastic methods.This brings the advantages of machine-learning potentials to key technological applications(e.g.,rechargeable batteries),which require an accurate description of the evolution of redox states.展开更多
基金support by the European Commission through the MaX Centre of Excellence for supercomputing applications(grant number 101093374)We gratefully acknowledge support from the Deutsche Forschungsgemeinschaft(DFG)under Germany’s Excellence Strategy(EXC 2077,No.390741603,University Allowance,University of Bremen)Lucio Colombi Ciacchi,the host of the“U Bremen Excellence Chair Program.”We acknowledge support by the NCCR MARVEL,a National Centre of Competence in Research,funded by the Swiss National Science Foundation(grant number 205602).
文摘While the accurate description of redox reactions remains a challenge for first-principles calculations,it has been shown that extended Hubbard functionals(DFT+U+V)can provide a reliable approach,mitigating self-interaction errors,in materials with strongly localized d or f electrons.Here,we first show that DFT+U+V molecular dynamics is capable of following the adiabatic evolution of oxidation states over time,using representative Li-ion cathode materials.In turn,this allows to develop redoxaware machine-learning potentials.Weshowthat considering atoms with different oxidation states(as accurately predicted by DFT+U+V)as distinct species in the training leads to potentials that are able to identify the correct ground state and pattern of oxidation states for redox elements present.This can be achieved,e.g.,through a systematic combinatorial search for the lowest-energy configuration or with stochastic methods.This brings the advantages of machine-learning potentials to key technological applications(e.g.,rechargeable batteries),which require an accurate description of the evolution of redox states.
