Exploring the structural and conformational properties of dioxygen dihalides (halogen = F, Cl, Br)
Bibliographic record
Abstract
The structural and conformational properties of dioxygen difluoride (1), dioxygen dichloride (2), and dioxygen dibromide (3) have been investigated by means of the hybrid density functional theory (B3LYP) and the hybrid meta exchange-correlation functional (M06-2X) with the aug-cc-pVQZ, aug-cc-pVTZ, cc-pVTZ, and 6-311++G** basis sets and natural bond orbital interpretation. The results obtained showed that the rotation at the O–O bond by passing from the plane symmetrical trans-(C2h) (or cis-(C2v)) form leads to the O–F bonds breaking. The natural bond order analysis revealed that the O–O bonds in the C2h and C2v forms of compound 1 possess double bond characters and the small bond orders between the oxygen and fluorine atoms results from the strong electron delocalization between the lone pairs of the fluorine atoms (LP4F) and the antibonding orbitals of the adjacent O–O double bond (π*O–O). The lengthening and shortening of the O–F and O–O bonds, respectively, in the trans-(C2h) or cis-(C2v) forms of compound 1 can be interpreted by the decrease of the bonding interactions between the fluorine and oxygen orbitals. The profiles of the orbital amplitudes (or electron densities) of O–O and O–F bonds in the C2h and C2v forms of compound 1 revealed that there are strong electronic repulsions between the πO–O and the lone pairs of oxygen atoms with the lone pairs of fluorine atoms, leading to the dissociation of O–F bonds. It is worth noting that there are strong hyperconjugative interactions between LP2O and the antibonding orbitals of adjacent O–F bonds (σ*O–F) in the skew (C2) form of compound 1, leading to the decrease of the O–O bond length and the increase of the F–O bond length by increasing the πO-O bonding and the σ*O–F antibonding orbital occupations. The increase of the electron delocalization from LP3F to σ*O–O with the decrease of the σ*O–O–σO–O energy gap (results from the increase of the O–O bond length) justifies the similarity between the adiabatic O–O bond dissociation energies in compound 1 and HOOH. The electron delocaizations from LP2O2 to σ*O3–X (X = F (1), Cl (2), Br (3)) decrease drastically from the skew ground state (C2) forms of compound 1 to compound 2 but increase slightly from compound 2 to compound 3, causing the significant increase of the O–O bond length ongoing from compound 1 to compound 2 and the slight decrease from compound 2 to compound 3. Effectively, the conformational properties of compounds 1–3 can be interpreted with the principle of maximum softness.
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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".