Benchmarking total energies with Hund's J terms in Hubbard-corrected spin-crossover chemistry
Fuente:
arXiv
Salvato in:
| Autori principali: | , , , |
|---|---|
| Natura: | Preprint |
| Pubblicazione: |
2025
|
| Soggetti: | |
| Accesso online: | |
| Tags: |
Aggiungi Tag
Nessun Tag, puoi essere il primo ad aggiungerne!!
|
| _version_ | 1866911090013634560 |
|---|---|
| author | MacEnulty, Lórien de Mendonça, João Paulo Almeida Poloni, Roberta O'Regan, David D. |
| author_facet | MacEnulty, Lórien de Mendonça, João Paulo Almeida Poloni, Roberta O'Regan, David D. |
| contents | The effect of the Hund's J terms in various DFT+U+J corrections to semi-local spin-density functional theory is assessed for a series of four octahedrally coordinated Fe(II) spin-crossover molecules spanning the covalent end of the ligand field spectrum. We report values and analyze trends for the Hubbard U and Hund's J parameters determined via minimum-tracking linear response for all valence atomic subspaces and relevant spin states in these molecules. We then methodically apply them via simplified rotationally-invariant Hubbard functionals in search of the simplest combination to yield reliable adiabatic energy differences with respect to those obtained using CASPT2/CC. The observed failure of canonical, positively-signed Hund's J terms in furthering the already robust capacity of DFT+U to obtain accurate energetics prompts an evaluation of their limitations when seeking to account for the static correlation phenomena in such strongly covalent systems and suggests directions for their improvement. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2508_01979 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Benchmarking total energies with Hund's J terms in Hubbard-corrected spin-crossover chemistry MacEnulty, Lórien de Mendonça, João Paulo Almeida Poloni, Roberta O'Regan, David D. Strongly Correlated Electrons Materials Science Chemical Physics Computational Physics The effect of the Hund's J terms in various DFT+U+J corrections to semi-local spin-density functional theory is assessed for a series of four octahedrally coordinated Fe(II) spin-crossover molecules spanning the covalent end of the ligand field spectrum. We report values and analyze trends for the Hubbard U and Hund's J parameters determined via minimum-tracking linear response for all valence atomic subspaces and relevant spin states in these molecules. We then methodically apply them via simplified rotationally-invariant Hubbard functionals in search of the simplest combination to yield reliable adiabatic energy differences with respect to those obtained using CASPT2/CC. The observed failure of canonical, positively-signed Hund's J terms in furthering the already robust capacity of DFT+U to obtain accurate energetics prompts an evaluation of their limitations when seeking to account for the static correlation phenomena in such strongly covalent systems and suggests directions for their improvement. |
| title | Benchmarking total energies with Hund's J terms in Hubbard-corrected spin-crossover chemistry |
| topic | Strongly Correlated Electrons Materials Science Chemical Physics Computational Physics |
| url | https://arxiv.org/abs/2508.01979 |