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CH3CH2-S-CH2CH2Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in 2-Chloroethyl ethyl sulfide
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Complete nqcc tensors for both 35Cl and 37Cl
in both GGT and TGT structural conformations of 2-chloroethyl ethyl
sulfide (CEES) have been determined by Tubergen et al. [1].
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Calculation was made here of
the nqcc tensors on PBE1PBE/6-311+G(3d,3p) optimized molecular
structures of these two conformers. Calculated and experimental
nqcc's are compared in Tables 1 - 4. Heavy atom structure
parameters and atomic coordinates respectively are given in Tables 5
and 6. Rotational constants are compared in Table 7.
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GGT/CEES I |
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TGT/CEES II |
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In Tables 1 - 4, subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor.
Ø (degrees) is the angle between the principal z-axis of the nqcc tensor and the CCl bond axis. ETA = (Xxx - Xyy)/Xzz. |
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's (percentage of the
average of the magnitudes of the experimental nqcc's). RSD is the
calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of the nqcc's. |
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Table 1.
35Cl
nqcc's in 2-Chloroethyl ethyl sulfide (MHz). Calculation was made
on the PBE1PBE/6-311+G(3d,3p) optimized structure of the GGT conformer. Expt. = CEES I. |
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Calc. |
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Expt. [1]
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35Cl |
Xaa |
- |
45.42 |
- |
44.8247(15) |
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Xbb |
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20.70
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20.8456(13)
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Xcc |
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24.72 |
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23.9791(20) |
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Xab * |
- |
35.29 |
- |
34.345(4) |
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Xac |
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28.29 |
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29.093(18) |
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Xbc |
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12.72 |
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12.77(4) |
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RMS |
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0.56 (1.9 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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34.67 |
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34.602(17) ** |
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Xyy |
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36.12 |
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35.618(21) |
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Xzz |
-
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70.79
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-
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70.220(14)
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ETA |
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0.0204 |
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0.0145(4) |
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Øz,CCl |
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0.28 |
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0.96 |
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* Algebraic signs of the off-diagonal
nqcc's depend on the positive/negative sense of the inertial axes,
which choice is arbitrary. The signs given here correspond to the
a,b,c coordinates defined in Table 6. As for the algebraic signs
of the experimental components, only the algebraic sign of the
product XabXacXbc can be
determined, which is reported as negative [1]. I have taken the
liberty of signing these to correspond to the calculated nqcc's. |
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** Calculated here with Z.Kisiel's QDIAG.f [2]. |
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These notes apply also to Tables 2 - 4. |
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Table 2.
37Cl
nqcc's in 2-Chloroethyl ethyl sulfide (MHz). Calculation was made on the
PBE1PBE/6-311+G(3d,3p) optimized structure of the GGT conformer. Expt. = CEES I. |
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Calc. |
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Expt. [1]
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37Cl |
Xaa |
- |
36.06 |
- |
35.589(4) |
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Xbb |
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16.55
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16.6635(28)
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Xcc |
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19.50 |
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18.926(5) |
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Xab * |
- |
27.59 |
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26.84(5) |
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Xac |
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22.31 |
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23.00(8) |
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Xbc |
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9.92 |
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9.98(4) |
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RMS |
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0.43 (1.8 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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27.33 |
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27.304(60) ** |
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Xyy |
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28.47 |
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28.075(36) |
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Xzz |
-
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55.79
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-
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55.378(56)
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ETA |
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0.0204 |
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0.0139(13) |
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Øz,CCl |
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0.28 |
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0.99 |
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Table 3.
35Cl
nqcc's in 2-Chloroethyl ethyl sulfide (MHz). Calculation was made on
the PBE1PBE/6-311+G(3d,3p) optimized structure of the TGT conformer. Expt. = CEES II. |
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Calc. |
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Expt. [1]
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35Cl |
Xaa |
- |
57.40 |
- |
56.661(2) |
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Xbb |
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34.57
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34.289(18)
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Xcc |
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22.83 |
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22.372(18) |
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Xab * |
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11.18 |
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10.31(4) |
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Xac |
- |
33.54 |
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33.70(8) |
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Xbc |
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3.41 |
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3.2(16) |
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RMS |
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0.52 (1.4 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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34.69 |
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34.46(134) ** |
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Xyy |
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36.18 |
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35.73(123) |
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Xzz |
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70.86
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70.19(12)
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ETA |
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0.0210 |
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0.018(26) |
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Øz,CCl |
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0.29 |
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0.79 |
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Table 4.
37Cl
nqcc's in 2-Chloroethyl ethyl sulfide (MHz). Calculation was made on
the PBE1PBE/6-311+G(3d,3p) optimized structure of the TGT conformer. Expt. = CEES II. |
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Calc. |
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Expt. [1]
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37Cl |
Xaa |
- |
45.32 |
- |
44.757(18) |
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Xbb |
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27.29
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27.079(9)
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Xcc |
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18.02 |
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17.678(20) |
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Xab * |
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8.61 |
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7.88(7) |
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Xac |
- |
26.40 |
- |
26.66(5) |
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Xbc |
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2.61 |
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0.4(4) |
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RMS |
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0.40 (1.3 %) |
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RSD |
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0.44 (1.1 %) |
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Xxx |
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27.34 |
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25.29(39) ** |
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Xyy |
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28.51 |
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29.99(36) |
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Xzz |
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55.85
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-
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55.281(45)
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ETA |
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0.0210 |
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0.0849(96) |
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Øz,CCl |
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0.29 |
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1.20 |
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| Table 5. 2-Chloroethyl ethyl sulfide. Heavy atom molecular structure parameters (Å
and degrees). See Z-Matrices for complete structure parameters. |
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GGT |
TGT |
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Z-Matrix GGT
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ClC(4) |
1.7934 |
1.7930 |
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C(4)C(3) |
1.5114 |
1.5116 |
| Z-Matrix TGT |
C(3)S |
1.8074 |
1.8062 |
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SC(2) |
1.8129 |
1.8130 |
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C(2)C(1) |
1.5172 |
1.5180 |
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ClC(4)C(3) |
110.84 |
110.82 |
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C(4)C(3)S |
111.46 |
111.90 |
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C(3)SC(2) |
101.64 |
101.02 |
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SC(2)C(1) |
114.42 |
109.28 |
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| Table 6. 2-Chloroethyl
ethyl sulfide. Heavy atom atomic coordinates. (More figures
are shown than are significant.) |
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a (Å) |
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b (Å) |
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c (Å) |
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| GGT |
Cl |
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2.749287 |
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0.369985 |
- |
0.027207 |
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C |
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1.182246 |
- |
0.310299 |
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0.518452 |
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C |
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0.192132 |
- |
0.362099 |
- |
0.622322 |
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S |
- |
1.402305 |
- |
1.022067 |
- |
0.084770 |
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C |
- |
2.165977 |
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0.437733 |
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0.671912 |
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C |
- |
2.647051 |
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1.479643 |
- |
0.320540 |
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| TGT |
Cl |
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2.895356 |
- |
0.313137 |
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0.057306 |
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C |
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1.217978 |
- |
0.110336 |
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0.542846 |
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C |
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0.375673 |
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0.643557 |
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0.460771 |
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S |
- |
1.325643 |
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0.852168 |
- |
0.108874 |
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C |
- |
2.020034 |
- |
0.779534 |
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0.268245 |
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C |
- |
3.495090 |
- |
0.791504 |
- |
0.090088 |
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| Table 7. 2-Chloroethyl ethyl sulfide. Rotational Constants (MHz). 35Cl Species. |
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Calc. ropt |
Expt. [1] |
Calc. ropt |
Expt. [1] |
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GGT |
CEES I |
TGT |
CEES II |
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| A |
4611.2 |
4550.8330(4) |
6846.8 |
6762.8209(11) |
| B |
919.5 |
925.74787(8) |
796.0 |
798.25329(15) |
| C |
832.2 |
835.20092(7) |
747.2 |
747.99297(14) |
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[1] M.J.Tubergen, A.Lesarri, R.D.Suenram, A.C.Samuels, J.O.Jensen, M.W.Ellzy, J.M.Lochner, J.Mol.Spectrosc. 233,180(2005).
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[2] Z.Kisiel, PROSPE - Programs for ROtational SPEctroscopy, http://info.ifpan.edu.pl/~kisiel/prospe.htm. |
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CH3CH2Cl |
1-Chloro-2-Fluoroethane |
1-Chloropropane |
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CH3Cl |
1-Chloro-1-Fluoroethane |
2-Chloroethanol |
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Table of Contents |
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Molecules/Chlorine |
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CEES.html |
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Last
Modified 7 Jan 2006 |
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