A perspective on the relative merits of time‐dependent and time‐independent density functional theory in studies of the electron spectra due to transition metal complexes. An illustration through applications to copper tetrachloride and plastocyanin
Bibliographic record
Abstract
Evaluation of the excitation energies in and plastocyanin was carried out with three different density functional theory (DFT) methods: time‐dependent DFT (TDDFT), ΔDFT, and Δself consistent field (SCF)‐DFT. Use was made of two local (local density approximation and BP86), two hybrid (B3LYP and PBE0), and one long‐range corrected (LC‐BP86) functionals to probe the effect of the exact exchange on the excitation energies. Some well‐known deficiencies observed in TDDFT were explained on the basis of lacking orbital relaxation and two‐electron terms not considered in adiabatic TDDFT. Δself consistent field (SCF)‐DFT reproduces well the position of the charge‐transfer excitations and yields results in best agreement with experiment regardless of the system or functional used. We conclude that the orbital relaxation and proper account of higher‐order terms neglected in adiabatic TDDFT are of great importance for the simulation of excitation spectra. © 2014 Wiley Periodicals, Inc.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.006 | 0.004 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.002 |
| Scholarly communication | 0.002 | 0.002 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.002 | 0.003 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
Machine scores (provisional)
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.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".