Accurate crystal field Hamiltonians of single-ion magnets at mean-field cost

Fuente: arXiv
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Autori principali: Peng, Linqing, Liu, Shuanglong, Zhang, Xing, Chen, Xiao, Li, Chenghan, Cheng, Hai-Ping, Chan, Garnet Kin-Lic
Natura: Preprint
Pubblicazione: 2025
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author Peng, Linqing
Liu, Shuanglong
Zhang, Xing
Chen, Xiao
Li, Chenghan
Cheng, Hai-Ping
Chan, Garnet Kin-Lic
author_facet Peng, Linqing
Liu, Shuanglong
Zhang, Xing
Chen, Xiao
Li, Chenghan
Cheng, Hai-Ping
Chan, Garnet Kin-Lic
contents The effective crystal field Hamiltonian provides the key description of the electronic properties of single-ion magnets, but obtaining its parameters from ab initio computation is challenging. We introduce a simple approach to derive the effective crystal field Hamiltonian through density functional calculations of randomly rotated mean-field states within the low-energy manifold. In benchmarks on five lanthanide-based complexes, we find that we compute with mean-field cost an effective crystal field Hamiltonian that matches the state-of-the-art from much more expensive multi-configurational quantum chemistry methods. In addition, we are able to reproduce the experimental low-energy spectrum and magnetic properties with an accuracy exceeding prior attempts. Due to its low cost, our approach provides a crucial ingredient in the computational design of single-ion magnets with tailored physical properties and low-energy spectra.
format Preprint
id arxiv_https___arxiv_org_abs_2505_16905
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Accurate crystal field Hamiltonians of single-ion magnets at mean-field cost
Peng, Linqing
Liu, Shuanglong
Zhang, Xing
Chen, Xiao
Li, Chenghan
Cheng, Hai-Ping
Chan, Garnet Kin-Lic
Chemical Physics
Materials Science
Strongly Correlated Electrons
Computational Physics
Quantum Physics
The effective crystal field Hamiltonian provides the key description of the electronic properties of single-ion magnets, but obtaining its parameters from ab initio computation is challenging. We introduce a simple approach to derive the effective crystal field Hamiltonian through density functional calculations of randomly rotated mean-field states within the low-energy manifold. In benchmarks on five lanthanide-based complexes, we find that we compute with mean-field cost an effective crystal field Hamiltonian that matches the state-of-the-art from much more expensive multi-configurational quantum chemistry methods. In addition, we are able to reproduce the experimental low-energy spectrum and magnetic properties with an accuracy exceeding prior attempts. Due to its low cost, our approach provides a crucial ingredient in the computational design of single-ion magnets with tailored physical properties and low-energy spectra.
title Accurate crystal field Hamiltonians of single-ion magnets at mean-field cost
topic Chemical Physics
Materials Science
Strongly Correlated Electrons
Computational Physics
Quantum Physics
url https://arxiv.org/abs/2505.16905