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CH2=CBr-CH3
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in 2-Bromopropene
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Calculation of the Br nqcc tensors
in 2-bromopropene was made here on molecular structures given by
MP2/aug-cc-pVTZ(G03) and
MP2/6-311+G(3df,3pd) optimizations; and on these
same structures but with ~re C-C, C=C, and CBr bond
lengths. These calculated nqcc's are compared
with the experimental values [1] 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. Ø (degrees) is the
angle between its subscripted parameters. 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,3p) 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. 79Br
nqcc's in 2-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/aug-cc-pVTZ(G03) optimized molecular structure. |
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Calc (2) was made on this same
structure but with ~re C-C, C=C, and CBr 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 |
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536.78 |
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539.31 |
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534.474(53) |
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Xbb |
- |
289.25 |
- |
289.71 |
- |
286.348(56) |
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Xcc |
- |
247.53 |
- |
249.60 |
- |
248.126(56) |
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|Xab| |
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52.28 |
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52.60 |
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RMS |
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2.17 (0.61 %) |
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3.50 (0.98 %) |
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RSD |
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1.58 (0.39 %) |
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1.58 (0.39 %) |
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Xxx |
- |
292.54 |
- |
293.04 |
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Xyy |
- |
247.53 |
- |
249.60 |
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Xzz |
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540.07 |
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542.64 |
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ETA |
- |
0.0834 |
- |
0.0800 |
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Øz,a |
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3.61 |
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3.62 |
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Øa,CBr |
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3.50 |
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3.53 |
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Øz,CBr |
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0.10 |
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0.08 |
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Table 2. 81Br
nqcc's in 2-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/aug-cc-pVTZ(G03) optimized molecular structure. |
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Calc (2) was made on this same
structure but with ~re C-C, C=C, and CBr 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 |
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448.48 |
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450.60 |
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446.653(71) |
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Xbb |
- |
241.68 |
- |
242.06 |
- |
239.100(80) |
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Xcc |
- |
206.80 |
- |
208.54 |
- |
207.554(80) |
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|Xab| |
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43.54 |
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43.80 |
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RMS |
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1.88 (0.63 %) |
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2.90 (0.98 %) |
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RSD |
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1.38 (0.40 %) |
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1.38 (0.40 %) |
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Xxx |
- |
244.41 |
- |
244.82 |
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Xyy |
- |
206.80 |
- |
208.54 |
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Xzz |
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451.21 |
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453.36 |
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ETA |
- |
0.0834 |
- |
0.0800 |
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Øz,a |
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3.60 |
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3.60 |
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Øa,CBr |
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3.49 |
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3.52 |
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Øz,CBr |
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0.10 |
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0.08 |
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Table 3. 79Br
nqcc's in 2-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/6-311+G(3df,3pd) optimized molecular structure. |
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Calc (2) was made on this same
structure but with ~re C-C, C=C, and CBr 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 |
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539.04 |
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539.98 |
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534.474(53) |
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Xbb |
- |
289.97 |
- |
290.05 |
- |
286.348(56) |
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Xcc |
- |
249.07 |
- |
249.93 |
- |
248.126(56) |
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|Xab| |
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52.63 |
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52.86 |
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RMS |
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3.41 (0.96 %) |
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3.97 (1.11 %) |
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RSD |
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1.58 (0.39 %) |
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1.58 (0.39 %) |
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Xxx |
- |
293.30 |
- |
293.41 |
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Xyy |
- |
249.07 |
- |
249.93 |
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Xzz |
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542.36 |
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543.34 |
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ETA |
- |
0.0816 |
- |
0.0800 |
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Øz,a |
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3.62 |
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3.63 |
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Øa,CBr |
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3.51 |
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3.54 |
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Øz,CBr |
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0.10 |
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0.09 |
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* The algabraic sign of the product XabXacXbc is
positive. |
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Table 4. 81Br
nqcc's in 2-Bromopropene (MHz). |
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Calc (1) was made on the
MP2/6-311+G(3df,3pd) optimized molecular structure. |
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Calc (2) was made on this same
structure but with ~re C-C, C=C, and CBr 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 |
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450.37 |
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451.16 |
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446.653(71) |
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Xbb |
- |
242.28 |
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242.35 |
- |
239.100(80) |
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Xcc |
- |
208.09 |
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208.81 |
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207.554(80) |
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|Xab| |
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43.83 |
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44.02 |
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RMS |
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2.84 (0.95 %) |
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3.29 (1.10 %) |
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RSD |
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1.38 (0.40 %) |
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1.38 (0.40 %) |
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Xxx |
- |
245.04 |
- |
245.13 |
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Xyy |
- |
208.09 |
- |
208.81 |
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Xzz |
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453.13 |
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453.94 |
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ETA |
- |
0.0816 |
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0.0800 |
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Øz,a |
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3.61 |
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3.62 |
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Øa,CBr |
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3.50 |
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3.53 |
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Øz,CBr |
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0.10 |
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0.09 |
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| Table 5. 2-Bromopropene.
Heavy atom structure parameters
(Å and degrees). Complete r(1) structures are given here in Z-matrix format. |
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r (1) = MP2/aug-cc-pVTZ(G03)
opt. |
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r (2) = r (1) but
with ~re C-C, C=C, and CBr
bond lengths. |
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| Point Group Cs |
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r (1) |
r (2) |
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C(2)Br |
1.8922 |
1.9006 |
| C(2)C(3) |
1.4907 |
1.4900 |
| C(2)C(4) |
1.3328 |
1.3291 |
| C(3)C(2)Br |
114.06 |
114.06 |
| C(4)C(2)Br |
119.64 |
119.64 |
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| r (1) = MP2/6-311+G(3df,3pd)
opt. |
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C=C, and CBr bond lengths. |
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r (1) |
r (2) |
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| Click on image to enlarge. |
C(2)Br |
1.8972 |
1.9007 |
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C(2)C(3) |
1.4920 |
1.4913 |
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C(2)C(4) |
1.3327 |
1.3297 |
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C(3)C(2)Br |
114.21 |
114.21 |
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C(4)C(2)Br |
119.79 |
119.79 |
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| Table 6. 2-Bromopropene.
Rotational constants (MHz). 79Br species. |
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r (1) = MP2/aug-cc-pVTZ(G03)
opt. |
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r (2) = r (1) but
with ~re C-C, C=C, and CBr bond lengths. |
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r (1) |
r (2) |
Expt. [1] |
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A |
9 317.1 |
9 343.3 |
9 256.00(10) |
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B |
3 167.4 |
3 148.1 |
3 138.011(26) |
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C |
2 398.8 |
2 389.4 |
2 375.879(26) |
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r (1) = MP2/6-311+G(3df,3pd)
opt. |
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r (2) = r (1) but with ~re
C-C, C=C, and CBr bond length. |
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r (1) |
r (2) |
Expt. [1] |
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A |
9 331.6 |
9 353.4 |
9 256.00(10) |
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B |
3 147.3 |
3 140.1 |
3 138.011(26) |
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C |
2 388.2 |
2 385.4 |
2 375.879(26) |
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[1] E.Fliege and H.Dreizler, Z.Naturforsch. 39a,637(1984).
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H.P.Benz, A.Bauder, and
Hs.H.Günthard, J.Mol.Spectrosc. 21,165(1966): For 79Br, Xaa = 534.5(61), Xbb = -286.5(48), Xcc = -248.0(41), |Xab| = MHz; and for 81Br, Xaa = 446.6(35), Xbb = -239.0(25), Xcc = -207.6(33) MHz.
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2-Chloropropene |
gauche-3-Bromopropene
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Table of Contents |
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Molecules/Bromine |
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2BrPropene.html |
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Last
Modified 23 March 2009 |
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