Towards understanding performance differences between approximate density functionals for spin states of iron complexes
Why is this work in the frame?
A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.
No Canadian affiliation. An affiliation-only frame, the usual design, would never have seen this work. It is one of the works that make the case for inverting the frame.
Full frame distilled prediction
Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
- Candidate categories
- none
- Consensus categories
- none
- Domain
- Candidate signal: noneConsensus signal: none
- Study design
- Candidate signal: Bench or experimentalConsensus signal: Bench or experimental
- Genre
- Candidate signal: EmpiricalConsensus signal: Empirical
- Teacher disagreement score
- 0.124
- Threshold uncertainty score
- 0.372
- Validation status
machine_predicted_unvalidated·codex-gemma-dda1882f352a
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
- Teacher spread
- 0.208 · how far apart the two teachers sit on this one work
- Validation status
score_only:v0-immature-baseline· verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it
Abstract
Density functional theory has been widely used to investigate the structural and electronic properties of heme-containing proteins such as cytochrome P450. Nevertheless, recent studies have shown that approximate exchange-correlation energy density functionals can incorrectly predict the stability order of spin states in, for instance, iron-containing pyridine and imidazole systems. This raises questions about the validity of earlier theoretical studies. In this work, we systematically investigate a few typical inorganic and organic iron-containing complexes and try to understand the performance difference of various density functionals. Two oxidation states of iron, Fe(II) and Fe(III), with different spin states and both adiabatic and vertical structures are considered. A different description of the outmost molecular orbital is found to play the crucial role. Local density and generalized gradient based functionals bias the lower spin state and produce a more localized frontier orbital that is higher in energy than the hybrid functionals. Energy component analysis has been performed, together with comparison of numerous structural and electronic properties. Implications of the present work to the theoretical study of heme-containing biological molecules and other spin-related systems are discussed.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
The record
- Venue
- The Journal of Chemical Physics
- Topic
- Metal-Catalyzed Oxygenation Mechanisms
- Field
- Chemistry
- Canadian institutions
- not available
- Funders
- Chinese Academy of SciencesDebreceni EgyetemMcMaster University
- Keywords
- Spin statesDensity functional theorySpin (aerodynamics)Spin densityDensity of statesAdiabatic processWork (physics)Molecular orbitalStatistical physicsChemical physicsChemistryPhysicsComputational chemistryMoleculeMaterials scienceCondensed matter physicsQuantum mechanicsThermodynamics
- Has abstract in OpenAlex
- yes