Gas-Phase Oxidation and Nitration of First-, Second-, and Third-Row Atomic Cations in Reactions with Nitrous Oxide: Periodicities in Reactivity
Bibliographic record
Abstract
Room-temperature reactions of 46 different atomic cations with N 2 O have been surveyed systematically using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. The atomic cations are produced at about 5500 K in the ICP source and are allowed to decay radiatively and thermalize by collisions with Ar and He atoms prior to reaction. Rate coefficients were measured for the reactions of first-row atomic cations from K + to Se +, of second-row atomic cations from Rb + to Te + (excluding Tc + ), and of third-row atomic cations from Cs + to Bi + . Primary reaction channels were observed corresponding to O-atom transfer, N-atom transfer, and N 2 O addition. Periodicities were observed in overall reaction efficiency, and these are scrutinized in terms of overall exothermicity, the presence of an activation barrier in the reaction coordinate, and the overall conservation of spin. N-atom transfer was observed to compete with O-atom transfer in the reactions of N 2 O with La + (4%), Ti + (22%), Zr + (45%), Nb + (35%), Ta + (40%), and Os + (60%). Up to three N 2 O molecules were observed to add sequentially to selected atomic cations as well as several monoxide and dioxide cations. A second O-atom transfer was observed with the group 4, 5, and 6 transition-metal ions (except Mo + ) as well as the third-row cations Re +, Os +, Ir +, and Pt + . The atomic ions W +, Os +, and Ir + formed trioxides in sequential O-atom transfer reactions, and Os + even formed the tetroxide OsO 4 + . Multicollision-induced dissociation studies with Ar buffer gas indicated thermodynamically controlled dissociation of TiO 2 +, ZrO 2 +, HfO 2 +, VO 2 +, NbO 2 +, TaO 2 +, and WO 2 + by the consecutive detachment of O-atoms while CrO 2 +, ReO 2 +, and PtO 2 + decomposed primarily by loss of O 2 molecules.
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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 | 0.000 | 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) | 0.001 | 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".