|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH2CH2CHBr |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Bromine |
|
|
|
Nuclear
Quadrupole Coupling Constants |
|
|
|
in Cyclopropyl Bromide |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Calculation of the bromine nqcc's
in cyclopropyl bromide was made on molecular structures given by
MP2 and PBE1PBE optimizations each in conjunction with 6-31G(3d,3p) and aug-cc-pVTZ(G03) bases. These
are
compared with the experimental nqcc's in Tables 1 - 4.
Structure parameters are compared in Table 5, rotational
constants in Table 6. |
|
|
|
|
|
|
|
|
|
|
|
|
In Tables 1 - 4, subscripts a,b,c refer to the
principal axes of the inertia tensor, subscripts x,y,z to the principal axes
of the nqcc tensor. The nqcc y-axis is chosen coincident with the
inertia b-axis, these are perpendicular to the molecular symmetry plane.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
|
|
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 for the B1LYP/TZV(3df,3p) model
for calculation of the nqcc's. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 1. 79Br
nqcc's in Cyclopropyl Bromide (MHz). Calculation was made on the
(1) MP2/6-31G(3d,3p) and (2) MP2/aug-cc-pVTZ(G03) optimized molecular
structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1)
|
|
Calc (2) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
464.47 |
|
466.28 |
|
463.87(23) |
|
|
Xbb |
- |
288.10 |
- |
287.21 |
- |
284.88 * |
|
|
Xcc |
- |
176.37 |
- |
179.08 |
- |
178.99 * |
|
|
|Xac| |
|
269.07 |
|
264.73 |
|
266.36(34) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
2.42 (0.78 %) |
1.94 (0.63 %) |
|
|
|
RSD |
|
1.58 (0.39 %) |
1.58 (0.39 %) |
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
274.36 |
- |
273.77 |
|
|
|
|
Xyy |
- |
288.10 |
- |
287.21 |
|
|
|
|
Xzz |
|
562.46 |
|
560.98 |
|
|
|
|
ETA |
|
0.0244 |
|
0.0239 |
|
|
|
|
Øz,a |
|
20.01 |
|
19.68 |
|
|
|
|
Øa,CBr |
|
19.20 |
|
19.02 |
|
|
|
|
Øz,CBr |
|
0.81 |
|
0.66 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calculated here from experimental Xaa and Xbb - Xcc = - 105.893(73) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 2. 81Br
nqcc's in Cyclopropyl Bromide (MHz). Calculation was made on the (1)
MP2/6-31G(3d,3p) and (2) MP2/aug-cc-pVTZ(G03) optimized molecular
structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1)
|
|
Calc (2) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
388.20 |
|
389.71 |
|
388.18(22) |
|
|
Xbb |
- |
240.70 |
- |
239.95 |
- |
238.24 * |
|
|
Xcc |
- |
147.50 |
- |
149.76 |
- |
149.94 * |
|
|
|Xac| |
|
224.62 |
|
220.99 |
|
222.02(31) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
2.00 (0.77 %) |
1.33 (0.51 %) |
|
|
|
RSD |
|
1.38 (0.40 %) |
1.38 (0.40 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calculated here from experimental Xaa and Xbb - Xcc = - 88.298(74) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 3. 79Br
nqcc's in Cyclopropyl Bromide (MHz). Calculation was made on the
(1) PBE1PBE/6-31G(3d,3p) and (2) PBE1PBE/aug-cc-pVTZ(G03) optimized
molecular structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1)
|
|
Calc (2) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
465.95 |
|
476.59 |
|
463.87(23) |
|
|
Xbb |
- |
286.57 |
- |
287.85 |
- |
284.88 * |
|
|
Xcc |
- |
179.38 |
- |
188.74 |
- |
178.99 * |
|
|
|Xac| |
|
264.01 |
|
255.58 |
|
266.36(34) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
1.56 (0.51 %) |
9.41 (3.04 %) |
|
|
|
RSD |
|
1.58 (0.39 %) |
1.58 (0.39 %) |
|
|
|
|
|
|
|
|
|
|
|
|
Xxx |
- |
273.63 |
- |
275.58 |
|
|
|
|
Xyy |
- |
286.57 |
- |
287.85 |
|
|
|
|
Xzz |
|
560.20 |
|
563.43 |
|
|
|
|
ETA |
|
0.0231 |
|
0.0218 |
|
|
|
|
Øz,a |
|
19.64 |
|
18.77 |
|
|
|
|
Øa,CBr |
|
19.02 |
|
18.50 |
|
|
|
|
Øz,CBr |
|
0.63 |
|
0.27 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calculated here from experimental Xaa and Xbb - Xcc = - 105.893(73) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| |
|
|
|
|
|
|
|
|
|
Table 4. 81Br
nqcc's in Cyclopropyl Bromide (MHz). Calculation was made on the
(1) PBE1PBE/6-31G(3d,3p) and (2) PBE1PBE/aug-cc-pVTZ(G03) optimized
molecular
structures. |
|
| |
|
|
|
|
|
|
|
|
|
|
|
Calc (1)
|
|
Calc (2) |
|
Expt. [1] |
|
| |
|
|
|
|
|
|
|
|
|
Xaa |
|
389.43 |
|
398.32 |
|
388.18(22) |
|
|
Xbb |
- |
239.42 |
- |
240.49 |
- |
238.24 * |
|
|
Xcc |
- |
150.01 |
- |
157.83 |
- |
149.94 * |
|
|
|Xac| |
|
220.40 |
|
213.35 |
|
222.02(31) |
|
|
|
|
|
|
|
|
|
|
|
RMS |
|
1.00 (0.39 %) |
7.53 (2.91 %) |
|
|
|
RSD |
|
1.38 (0.40 %) |
1.38 (0.40 %) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
* Calculated here from experimental Xaa and Xbb - Xcc = - 88.298(74) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 5.
Cyclopropyl Bromide. Heavy atom structure parameters
(Å and degrees). Complete structures are given here in Z-Matrix format. |
| |
|
|
|
| ropt(1) = MP2/6-31G(3d,3p) optimization. |
| ropt(2) = MP2/aug-cc-pVTZ optimization. |
| ropt(3) = PBE1PBE/6-31G(3d,3p) optimization. |
| ropt(4) = PBE1PBE/aug-cc-pVTZ optimization. |
| |
|
|
|
|
|
ropt (1) |
ropt (2) |
|
|
|
|
|
C(1)Br |
1.9013 |
1.8987 |
|
C(1)C(2,3) |
1.4955 |
1.4947 |
|
C(2)C(3) |
1.5144 |
1.5133 |
|
C(2,3)C(1)Br |
118.37 |
118.84 |
|
C(2)C(1)C(3) |
60.84 |
60.82 |
| |
|
|
|
|
|
ropt (3) |
ropt (4) |
|
|
|
|
|
C(1)Br |
1.8981 |
1.9136 |
|
C(1)C(2,3) |
1.4894 |
1.4875 |
|
C(2)C(3) |
1.5059 |
1.5044 |
|
C(2,3)C(1)Br |
118.80 |
119.80 |
|
C(2)C(1)C(3) |
60.73 |
60.75 |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
| Table 6. Cyclopropyl Bromine. Rotational Constants (MHz). Normal Species. |
| |
|
|
|
|
| ropt(1) = MP2/6-31G(3d,3p) optimization. |
| ropt(2) = MP2/aug-cc-pVTZ optimization. |
| ropt(3) = PBE1PBE/6-31G(3d,3p) optimization. |
| ropt(4) = PBE1PBE/aug-cc-pVTZ optimization. |
| |
|
|
|
|
|
ropt(1) |
ropt(2) |
ropt(3) |
ropt(4) |
|
|
|
|
|
| A |
16 410.4 |
16 479.8 |
16 523.0 |
16 647.1 |
| B |
2 616.2 |
2 612.7 |
2 618.7 |
2 573.6 |
| C |
2 493.3 |
2 489.1 |
2 495.7 |
2 452.9 |
|
|
|
|
|
| Expt. [1] A,B,C = 16334.244(17), 2579.92042(73), 2457.71592(36) MHz. |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
[1] H.Li, M.C.L.Gerry, and W.Lewis-Bevan, J.Mol.Spectrosc. 144,51(1990). |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Cyclopropyl Chloride |
1,1-Dichlorocyclopropane |
|
|
|
Cyclopropyl Cyanide |
(Chloromethyl)cyclopropane |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table of Contents |
|
|
|
|
|
Molecules/Bromine |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
CH2CH2CHBr.html |
|
|
|
|
|
|
Last
Modified 21 Sept 2006 |
|
|
|
|
|
|
|
|
|
|