A proposed new scheme for vibronically resolved time-dependent photoelectron spectroscopy: pump–repump-continuous wave-photoelectron spectroscopy (prp-cw-pes)
Bibliographic record
Abstract
We propose a new scheme for time-resolved photoelectron spectroscopy denoted as pump-repump-continuous wave-photoelectron spectroscopy (prp-cw-pes). This scheme is comprised of two femtosecond laser (pump) pulses under cw illumination (probe). By changing the time-delay between pump and repump lasers one can manipulate the populations of vibronic levels in electronic excited states. The cw laser acts on for a long time and establishes resonance between excited states and the continuum photo-ionized states. Sharp spectra can be obtained from the resonance condition [formula: see text]. The intensities in the spectra are sensitive to the time-delay between the pump-repump pulses, but only depend on the populations of excited states, not the phase relations (coherence). As a result, each time-delayed snapshot spectrum is a weighted sum of so-called fingerprints, where a fingerprint is the vibrationally resolved photoelectron spectrum for a single vibronic excited state. The latter information can potentially be simulated reliably using vibronic models and wave packet propagation methods. In the easiest application of the experiment, different time-delays produce different spectra, for a single molecular system. This wealth of experimental data can be fitted to an, ideally small, set of theoretical fingerprints by adjusting the populations as fitting parameters. This technique might be able to distinguish between closely related molecular species. Adopting a different viewpoint, the proposed scheme can also be employed to monitor the time-dependent dynamics by changing the phase relationship between the pump and repump laser that can be viewed as a "control mechanism" employed in wave packet interferometry. Simplifications arise as the change in the spectra is due to the changing populations, not because of the coherence. In this paper, we outline the ideas behind the scheme and illustrate the ideas theoretically using simple model systems.
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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 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.001 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.002 |
| Open science | 0.003 | 0.001 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.004 | 0.001 |
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".