Table 1.
Theoretically modelled 129Xe NMR chemical shift (δ) and anisotropy (CSA, Δδ) in ppm for the five most likely o‐fluorophenol CSP candidates in their PBE‐TS optimized structures, unless stated otherwise.
| oF_A | oF_B | oF_C | oF_D | oF_E | ||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Method | δ | Δδ | δ | Δδ | δ | Δδ | δ | Δδ | δ | Δδ |
| Cluster model [a] | ||||||||||
| PBE | 218.7 | −14.3 | 245.0 | −79.3 | 215.1 | 4.6 | 261.5 | −38.6 | 370.5 | 7.7 |
| BLYP | 226.5 | −14.6 | 253.4 | −81.8 | 222.5 | 4.1 | 270.9 | −40.2 | 381.5 | 7.9 |
| B3LYP | 195.9 | 23.1 | 223.1 | −75.6 | 195.9 | 0.9 | 240.8 | −36.6 | 338.1 | 13.1 |
| BHandHLYP | 165.8 | −21.3 | 190.7 | −68.3 | 162.6 | −1.2 | 209.9 | −35.8 | 288.5 | 18.3 |
| BHandHLYP[b] | 145.8 | −20.5 | 175.0 | −61.8 | 143.2 | 0.9 | 189.4 | −31.6 | 262.0 | 14.4 |
| BHandHLYP[c] | 174.9 | −11.6 | 192.3 | −71.2 | 171.3 | 6.7 | 216.7 | −31.6 | 292.0 | 31.1 |
| Periodic model [d] | ||||||||||
| PBE[e] | 195.1 | −28.1 | 272.1 | −66.4 | 238.7 | 7.0 | 288.8 | −26.2 | 362.1 | 23.1 |
| PBE | 229.8 | −38.9 | 273.2 | −86.7 | 236.4 | −15.4 | 285.0 | −46.5 | 402.7 | 2.0 |
| BLYP[f] | 237.3 | −39.1 | 281.5 | −89.3 | 243.6 | −15.9 | 294.3 | −48.1 | 413.6 | 2.1 |
| B3LYP[f] | 206.3 | −48.0 | 250.8 | −82.9 | 216.7 | −19.3 | 263.8 | −44.5 | 369.5 | 7.5 |
| BHandHLYP[f] | 175.6 | −46.3 | 217.7 | −75.4 | 182.6 | −21.5 | 232.3 | −43.6 | 318.8 | 12.7 |
| BHandHLYP[g] | 236.2 | −82.4 | 243.7 | −46.8 | ||||||
| BHandHLYP[h] | 237.8 | −85.4 | 250.5 | −42.6 | ||||||
| Experimental | 256.0 | −47.5 | ||||||||
[a] Scalar relativistic SR‐ZORA calculations of a cluster model of one clathrate cavity with ADF code73, 74 using Xe/other=jcpl/TZP basis sets.76 129Xe chemical shift (δ=σXe−atom−σ) with respect to free Xe atom shielding values (σXe−atom): PBE/BLYP/B3LYP/BHandHLYP=5752.2/5752.6/5752.1/5752.0 ppm. Δδ (CSA) defined in principal axis system (PAS) along the unique axis (perpendicular to the plane of O−H rings). Asymmetry parameter η=0 in all cavities due to the cylindrical symmetry. [b] As footnote [a], but at nonrelativistic (NR) level of theory with σXe−atom(BHandHLYP)=5643.4 ppm. [c] As footnote [a], but at relativistic spin‐orbit SO‐ZORA level of theory with σXe−atom(BHandHLYP)=6609.3 ppm. [d] Scalar relativistic GIPAW results obtained with CASTEP code.71, 72 All periodic 129Xe chemical shifts referenced to CASTEP/PBE value: σXe−atom=5926.3 ppm. [e] In the CSP optimized crystal geometry. [f] As footnote [d], but estimated by scaling GIPAW/PBE PAS components with factors obtained at SR‐ZORA level for cluster model resulting in data in footnote [a]. [g] Correction added to result of footnote [f] due to thermal averaging (AVE) over Xe motion at T=300 by MC‐NVT simulation (see text for details). [h] Relativistic spin‐orbit (SO) corrections obtained as difference of SO‐ZORA and SR‐ZORA calculations with ADF code added to result of footnote [g].