Table II.
solvent shifts for solutes:
| TSC (kJ/mol) | Dipolar (kJ/mol) | shift(cm−1) | (from eq 1a) | (1b) | obs. shift I | II | III | obs. Shift (Berlman) |
||
|---|---|---|---|---|---|---|---|---|---|---|
| Phenol | ||||||||||
| CH | 425.7 | −16.9 | 2090 | 310 | 279 | 4260 | 580 | 1230 | 2090 | |
| MeOH | 392.35 | −23.5 | 5333 | 1545 | 2344 | 3970 | 600 | 950 | 2230 | |
| H2O | 399 | −26.9 | 4569 | 1632 | 2500 | |||||
| AcNH2 | 385 | − 22.0 | 5268 | 1440 | 2130 | |||||
| ------------------------------- | ||||||||||
| Indole | ||||||||||
| CH | 405.2 | −21.2 | 2580 | 1216 | 434 | 4581 | 50(Lb) 2550(La) |
2710 | 1930 | |
| MeOH | 352.6 | −45.5 | 7803 | 5920 | 3650 | 6842† | 3340(La) | 4230 | 4100 | |
| H2O | 368.7 | −52.4 | 7036 | 6249 | 3890 | 4950 | 2100 | 2340 | 2530 | |
| AcNH2 | 350.9 | −42.1 | 7663 | 5533 | 3310 | |||||
| ------------------------------- | ||||||||||
| α-NaphthNH2 | ||||||||||
| CH | 339.3 | −7.4 | 1339 | 395 | 158 | 6175 | 2310 | 2770 | 2860 | |
| MeOH | 280.8 | −15.6 | 4975 | 1982 | 1330 | 8900† | 5700 | 5500 | 4120 | |
| H2O | 295 | −17.9 | 3980 | 2090 | 1420 | |||||
| AcNH2 | 280.5 | −14.6 | 4914 | 1847 | 1210 | |||||
| ------------------------------- | ||||||||||
TSC is the solute transition energy calculated according to eq 5 (the Thompson-Schweizer-Chandler model1,2), ‘dipolar’ is the S.S. calculated from equ 7. Total shift is listed under “shift”. Berlman's values of S.S. are in reference 10. I, II, III refer to the methods used to calculate the S.S. (see text).
†
measurement is in solvent ethanol, not methanol.