Excited state wavepacket dynamics in NO2 probed by strong-field ionization
Bibliographic record
Abstract
We present an experimental femtosecond time-resolved study of the 399 nm excited state dynamics of nitrogen dioxide using channel-resolved above threshold ionization (CRATI) as the probe process. This method relies on photoelectron-photoion coincidence and covariance to correlate the strong-field photoelectron spectrum with ionic fragments, which label the channel. In all ionization channels observed, we report apparent oscillations in the ion and photoelectron yields as a function of pump-probe delay. Further, we observe the presence of a persistent, time-invariant above threshold ionization comb in the photoelectron spectra associated with most ionization channels at long time delays. These observations are interpreted in terms of single-pump-photon excitation to the first excited electronic X̃ 2A1 state and multi-pump-photon excitations to higher-lying states. The short time delay (<100 fs) dynamics in the fragment channels show multi-photon pump signatures of higher-lying neutral state dynamics, in data sets recorded with higher pump intensities. As expected for pumping NO2 at 399 nm, non-adiabatic coupling was seen to rapidly re-populate the ground state following excitation to the first excited electronic state, within 200 fs. Subsequent intramolecular vibrational energy redistribution results in the spreading of the ground state vibrational wavepacket into the asymmetric stretch coordinate, allowing the wavepacket to explore nuclear geometries in the asymptotic region of the ground state potential energy surface. Signatures of the vibrationally “hot” ground state wavepacket were observed in the CRATI spectra at longer time delays. This study highlights the complex and sometimes competing phenomena that can arise in strong-field ionization probing of excited state molecular dynamics.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. 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.
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)
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 teacher head, 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".