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CF3-CH2-CHI-CH3
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Iodine |
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Nuclear
Quadrupole Coupling Constants |
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in
tg-3-Iodo-1,1,1-trifluorobutane
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Calculation of the 127I
nqcc tensor
in tg-1-Iodo-3,3,3-trifluoropropane
was made here on molecular structures
given by MP2/6-311+G(d,p),
MP2/6-311+G(2d,2p), MP2/6-311+G(3d,3p), and MP2/6-311+G(df,pd)
optimizations; and on these
same structures but with empirically
corrected
C-C, CF, and CH bond lengths. These calculated nqcc's are
compared with experimental values
in Tables 1 - 4. Structure
parameters are given in Table 5, rotational constants in Table 6. |
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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. Øz,CI
(degrees) is the
angle between the z- and CI bond axes. ETA = (Xxx -
Xyy)/Xzz. |
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RMS is the root mean square
difference between calculated and experimental diagonal nqcc's (percent
of the average of the absolute experimental nqcc's). RSD is the
calibration residual
standard deviation of
the B1LYP/6-311G(df,p) model for calculation of the nqcc's, which may
be taken as an estimate of the uncertainty in the calculated nqcc's. |
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Table 1. 127I
nqcc's in tg-3-Iodo-1,1,1-trifluorobutane
(MHz). |
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Calc (1) was made on the
MP2/6-311+G(d,p) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, CF, and CH bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
- |
1495.8 |
- |
1491.8 |
- |
1473.890(40) |
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Xbb |
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672.7 |
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672.3 |
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656.689(46) * |
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Xcc |
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823.1 |
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819.4 |
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817.2013(236) |
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Xab |
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788.8 |
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785.1 |
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801.934(44) ** |
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Xac |
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450.8 |
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450.6 |
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445.207(67) ** |
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Xbc |
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- 146.8 |
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- 145.8 |
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- 149.799(35) ** |
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RMS |
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16.0 (1.63 %)
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13.8 (1.40 %)
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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907.6 |
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904.0 |
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900.662(33) |
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Xyy |
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929.3 |
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927.1 |
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924.826(50) |
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Xzz |
- |
1836.9 |
- |
1831.2 |
- |
1825.488(49) |
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ETA |
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0.01180 |
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0.01262 |
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0.01324(3) |
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Øz,CI |
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0.53 |
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0.57 |
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* Calculated here from zero trace
condition of the nqcc tensor. This note applies also to Tables 2
- 4. |
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** Algebraic signs taken from
calculated values. This note applies also to Tables 2
- 4. |
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Table 2. 127I
nqcc's in tg-3-Iodo-1,1,1-trifluorobutane
(MHz). |
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Calc (1) was made on the
MP2/6-311+G(2d,2p) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, CF, and CH bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
- |
1488.1 |
- |
1486.4 |
- |
1473.890(40) |
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Xbb |
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675.7 |
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675.1 |
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656.689(46) * |
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Xcc |
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812.4 |
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811.3 |
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817.2013(236) |
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Xab |
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766.6 |
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766.8 |
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801.934(44) ** |
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Xac |
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454.8 |
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455.2 |
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445.207(67) ** |
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Xbc |
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- 144.7 |
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- 144.5 |
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- 149.799(35) ** |
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RMS |
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14.0 (1.42 %)
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13.3 (1.36 %)
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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898.9 |
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898.1 |
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900.662(33) |
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Xyy |
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919.8 |
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919.5 |
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924.826(50) |
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Xzz |
- |
1818.7 |
- |
1817.6 |
- |
1825.488(49) |
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ETA |
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0.01148 |
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0.01180 |
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0.01324(3) |
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Øz,CI |
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0.50 |
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0.51 |
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Table 3. 127I
nqcc's in tg-3-Iodo-1,1,1-trifluorobutane
(MHz). |
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Calc (1) was made on the
MP2/6-311+G(3d,3p) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, CF, and CH bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
- |
1486.8 |
- |
1484.2 |
- |
1473.890(40) |
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Xbb |
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675.7 |
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674.9 |
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656.689(46) * |
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Xcc |
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811.1 |
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809.3 |
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817.2013(236) |
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Xab |
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771.5 |
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771.0 |
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801.934(44) ** |
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Xac |
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461.4 |
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461.8 |
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445.207(67) ** |
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Xbc |
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- 147.7 |
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- 809.3 |
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- 149.799(35) ** |
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RMS |
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13.7 (1.40 %)
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12.9 (1.31 %)
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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900.2 |
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898.6 |
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900.662(33) |
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Xyy |
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922.7 |
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922.0 |
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924.826(50) |
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Xzz |
- |
1822.9 |
- |
1820.6 |
- |
1825.488(49) |
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ETA |
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0.01238 |
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0.01282 |
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0.01324(3) |
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Øz,CI |
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0.59 |
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0.61 |
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Table 4. 127I
nqcc's in tg-3-Iodo-1,1,1-trifluorobutane
(MHz). |
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Calc (1) was made on the
MP2/6-311+G(df,pd) optimized molecular structure. |
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Calc (2) was made on this same
structure but with empirically corrected C-C, CF, and CH bond lengths. |
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Calc (1) |
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Calc (2) |
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Expt [1] |
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Xaa |
- |
1478.1 |
- |
1477.1 |
- |
1473.890(40) |
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Xbb |
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668.4 |
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668.7 |
|
656.689(46) * |
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Xcc |
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809.7 |
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808.4 |
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817.2013(236) |
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Xab |
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778.3 |
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777.0 |
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801.934(44) ** |
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Xac |
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457.0 |
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457.3 |
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445.207(67) ** |
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Xbc |
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- 147.8 |
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- 147.5 |
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- 149.799(35) ** |
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RMS |
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8.4 (0.85 %)
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8.8 (0.89 %)
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RSD |
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15.2 (1.23 %) |
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15.2 (1.23 %) |
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Xxx |
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897.4 |
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896.4 |
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900.662(33) |
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Xyy |
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920.9 |
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920.5 |
|
924.826(50) |
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Xzz |
- |
1818.3 |
- |
1816.9 |
- |
1825.488(49) |
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ETA |
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0.01288 |
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0.01331 |
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0.01324(3) |
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Øz,CI |
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0.58 |
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0.60 |
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| Table 5. tg-3-Iodo-1,1,1-trifluorobutane.
Selected structure
parameters (Å and
degrees). Complete structures are given here in Z-matrix representation. |
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r (1) = MP2/6-311+G(d,p) opt |
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r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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| Point Group C1 |
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r (1) |
r (2) |
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C(1)C(2) |
1.5120 |
1.5051 |
| C(2)C(3) |
1.5295 |
1.5215 |
| C(3)C(4) |
1.5234 |
1.5158 |
| C(3)I |
2.1826 |
2.1826 |
| C(1)C(2)C(3) |
113.83 |
113.83 |
| C(2)C(3)C(4) |
115.11 |
115.11 |
| C(2)C(3)I |
107.49 |
107.49 |
| C(1)C(2)C(3)C(4) |
- 63.19 |
- 63.19 |
| C(1)C(2)C(3)I |
174.29 |
174.29 |
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| r (1) = MP2/6-311+G(2d,2p) opt |
| r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
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| C(1)C(2) |
1.5076 |
1.5051 |
| C(2)C(3) |
1.5230 |
1.5215 |
| C(3)C(4) |
1.5179 |
1.5158 |
| C(3)I |
2.1557 |
2.1557 |
| C(1)C(2)C(3) |
113.55 |
113.55 |
| C(2)C(3)C(4) |
115.00 |
115.00 |
| C(2)C(3)I |
107.72 |
107.72 |
| C(1)C(2)C(3)C(4) |
- 60.91 |
- 60.91 |
| C(1)C(2)C(3)I |
176.04 |
176.04 |
| |
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r (1) = MP2/6-311+G(3d,3p) opt |
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r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
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C(1)C(2) |
1.5098 |
1.5051 |
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C(2)C(3) |
1.5246 |
1.5215 |
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C(3)C(4) |
1.5188 |
1.5158 |
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C(3)I |
2.1712 |
2.1712 |
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C(1)C(2)C(3) |
113.31 |
113.31 |
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C(2)C(3)C(4) |
114.88 |
114.88 |
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C(2)C(3)I |
107.30 |
107.30 |
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C(1)C(2)C(3)C(4) |
- 62.58 |
- 62.58 |
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C(1)C(2)C(3)I |
175.33 |
175.33 |
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r (1) = MP2/6-311+G(df,pd) opt |
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r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
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C(1)C(2) |
1.5130 |
1.5051 |
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C(2)C(3) |
1.5256 |
1.5215 |
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C(3)C(4) |
1.5199 |
1.5158 |
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C(3)I |
2.1529 |
2.1529 |
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C(1)C(2)C(3) |
113.92 |
113.92 |
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C(2)C(3)C(4) |
114.94 |
114.94 |
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C(2)C(3)I |
107.62 |
107.62 |
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C(1)C(2)C(3)C(4) |
- 62.27 |
- 62.27 |
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C(1)C(2)C(3)I |
175.08 |
175.08 |
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| Table 6.
tg-3-Iodo-1,1,1-trifluorobutane.
Rotational constants
(MHz). |
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r (1) = MP2/6-311+G(d,p) opt |
|
r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
Expt [1] |
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A |
2941.4 |
2969.9 |
2930.12759(98) |
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B |
446.2 |
448.7 |
449.276659(138) |
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C |
420.9 |
423.4 |
423.278388(300) |
| |
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r (1) = MP2/6-311+G(2d,2p) opt |
|
r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
Expt [1] |
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A |
2978.8 |
2998.6 |
2930.12759(98) |
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B |
451.6 |
452.7 |
449.276659(138) |
|
C |
426.4 |
427.5 |
423.278388(300) |
| |
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r (1) = MP2/6-311+G(3d,3p) opt |
|
r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
Expt [1] |
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A |
2965.4 |
2989.0 |
2930.12759(98) |
|
B |
449.6 |
451.4 |
449.276659(138) |
|
C |
424.5 |
426.2 |
423.278388(300) |
| |
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|
r (1) = MP2/6-311+G(df,pd) opt |
|
r (2) = r (1) with
corrected C-C, CF, and CH bond lengths. |
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r (1) |
r (2) |
Expt [1] |
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A |
2984.1 |
2982.7 |
2930.12759(98) |
|
B |
452.2 |
453.6 |
449.276659(138) |
|
C |
426.7 |
428.1 |
423.278388(300) |
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[1]
S.A.Cooke, private communication. |
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t-CH3CH2CH2I |
g-CH3CH2CH2I |
CH3I |
CH3CH2I |
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g-CH2ICH2F |
CH3-O-CH2I |
CH3CHICH3 |
(CH3)2CHCH2I |
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t-CF3CF2CH2I |
t-CF3CF2CF2I |
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Table of Contents |
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Molecules/Iodine |
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CF3CH2CHICH3.html |
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Last
Modified 1 March 2011 |
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