Calculation of excitation energies of open-shell molecules with spatially degenerate ground states. II. Transformed reference via intermediate configuration Kohn-Sham time dependent density functional theory oscillator strengths and magnetic circular dichroism C terms
Bibliographic record
Abstract
An extension of the transformed reference via an intermediate configuration Kohn-Sham time dependent density functional theory (TRICKS-TDDFT) method for calculating the transition energies of molecules with spatially degenerate ground states is proposed that enables oscillator strengths to also be evaluated. The oscillator strengths are calculated starting from a description of the degenerate ground state and the excited states of interest in terms of linear combinations of Slater determinants based upon the F-vectors obtained in the TRICKS-TDDFT calculation. This approach for calculating oscillator strengths can also be applied to several other properties that involve excited states. An example of such a property, the C term of magnetic circular dichroism (MCD), is presented. The new method is illustrated through example calculations of the absorbance and MCD spectra of several octahedral and C(4v) d(5) transition metal complexes. The calculated transition energies and oscillator strengths are somewhat too low and too high, respectively, but these errors are within the range that would normally be expected for TDDFT calculations of this type. The calculations help to resolve some previously unexplained problems with the MCD spectra of the C(4v) complexes.
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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 | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 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".