Table 2.
Observed and calculated IR data (>400 cm−1) for CH3S(O)2OO•.
| νobsa | νcalb | Δν(16/18O)c | Δν(12/13C)c | Assignmentd | |||||
|---|---|---|---|---|---|---|---|---|---|
| Ar-matrix | Ne-matrix | N2-matrix | CCSD(T) | M06-2X | obs. | cal. | obs. | cal. | |
| n.o.e | 3052.9 | 3053.0 | 3182.3 | 3193.8 (4) | n.o.e | <0.1 | n.o.e | 12.2 | ν1, νas(CH3) |
| 3032.1 (3) | 3036.5 | 3035.5 | 3167.7 | 3186.7 (5) | <0.5 | <0.1 | 10.4 | 11.9 | ν2, νas(CH3) |
| 2938.7 (1) | 2958.0 | 2953.4 | 3054.2 | 3078.6 (2) | <0.5 | <0.1 | 2.6 | 2.6 | ν3, νs(CH3) |
| 1435.3 (98) | 1439.7 | 1432.4 | 1436.0 | 1494.4 (191) | 53.2 | 58.3 | −2.2 | <0.1 | ν4, νas(SO2) |
| 1431.7 (<1) | n.o.e | n.o.e | 1430.2 | 1459.4 (10) | n.o. | 1.3 | 0.6 | 2.1 | ν5, δ(CH3) |
| 1402.8 (60) | 1408.8 | 1403.3 | 1367.9 | 1449.2 (52) | −7.5 | −14.9 | 2.5 | 2.0 | ν6, δ(CH3) |
| 1320.9 (18) | 1324.4 | 1325.8 | 1317.2 | 1358.4 (34) | 1.7 | 1.9 | 9.6 | 9.9 | ν7, δ(CH3) |
| 1204.2 (100) | 1207.5 | 1203.1 | 1145.2 | 1255.6 (148) | 47.7 | 49.9 | 0.5 | 0.1 | ν8, νs(SO2) |
| 1078.2 (10) | 1080.6 | 1079.7 | 1061.5 | 1237.5 (34) | 59.6 | 70.6 | <0.5 | <0.1 | ν9, ν(OO) |
| 971.5 (2) | 975.4 | 973.4 | 966.8 | 990.6 (6) | n.o.e | 2.8 | 7.6 | 8.3 | ν10, ω(CH3) |
| 963.0 (18) | 965.3 | 964.9 | 960.2 | 978.7 (33) | 1.4 | 2.4 | 8.5 | 7.8 | ν11, ρ(CH3) |
| 767.7 (54) | 772.7 | 770.9 | 757.6 | 802.9 (82) | 7.5 | 8.8 | 8.9 | 9.0 | ν12, ν(CS) |
| 631.3 (12) | 637.9 | 632.1 | 621.2 | 685.9 (64) | 24.0 | 26.3 | 2.8 | 3.8 | ν13, ν(SO) |
| 513.1 (6) | 514.9 | 513.6 | 488.9 | 531.4 (48) | 17.6 | 18.5 | 3.0 | 2.3 | ν14, δ(SO2) |
| 479.4 (5) | 480.9 | 481.9 | 461.8 | 496.3 (49) | 16.0 | 16.9 | 2.7 | 2.7 | ν15, δ(SOO) |
aObserved band positions for the most intense matrix sites and relative intensities (in parentheses) based on integrated band areas.
bHarmonic IR frequencies (>400 cm−1) and intensities (km mol−1, in parentheses) for the IR fundamentals calculated at the CCSD(T)/aug-cc-pV(D + d)Z and M06-2X/6-311++G(3df,3pd) levels of theory. Complete list of the IR data is given in Supplementary Table 3.
cM06-2X/6-311++G(3df,3pd) calculated and observed 16/18O- and 12/13C-isotopic shifts.
dAssignment of the vibration modes based on the vibrational displacement vectors.
eNot observed due to overlap or low intensity.