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CHBr3 |
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Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in
Bromoform |
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The complete Br nqcc tensors in
bromoform were determined by Kisiel et al. [1], which authors also
derived an rz molecular structure. An ro
structure was derived by Williams et al. [2]. |
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Calculation of the bromine nqcc
tensors in bromoform were made here on these rz and ro
structures. They are compared in Tables
1 - 4 with the experimental nqcc's of Ref. [1]. Structure
parameters and atomic coordinates are given in Tables 5 and 6,
respectively. |
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In Tables 1 and 2, Xuu is
the component of the nqcc tensor along the threefold symmetry
axis. Corresponding to the atomic coordinates given below in
Table 5, Xvv and Xww are the components along the
v- and w- axes for the Br atom in the uv-plane. Subscripts x,y,z refer to the principal axes of the nqcc
tensor. The y-axis is chosen coincident with the w-axis.
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.
RSD is the residual standard deviation of calibration 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 CH79Br3 (MHz). Calculation
was made on the ro and rz structures. The subscripts in parentheses are the axes labels of
Ref. [1]. |
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Calc / ro |
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Calc / rz |
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Expt. [1] |
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Xuu(cc) |
- |
228.56 |
- |
234.82 |
- |
231.9631(33) |
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Xvv(aa) |
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544.23 |
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549.48 |
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543.8554(53) |
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Xww(bb) |
- |
315.67 |
- |
314.66 |
- |
311.8922(53) |
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Xuv(ac) |
- |
268.68 * |
- |
258.70 * |
- |
258.522(13) |
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RMS |
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2.94 (0.81 %) |
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3.98 (1.10 %) |
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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 |
- |
312.79 |
- |
312.49 |
- |
310.2161(78) |
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Xyy |
- |
315.67 |
- |
314.66 |
- |
311.8922(53) |
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Xzz |
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628.46 |
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627.12 |
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622.1083(87) |
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ETA |
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0.0046 |
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0.00349 |
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0.002694(15) |
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Øz,u |
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72.59 |
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73.293 |
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73.1593(7) |
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Øu,CBr |
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71.89 |
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72.378 |
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Øz,CBr |
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0.70 |
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0.915 |
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* The algebraic sign corresponds to
the atomic coordinates given in Table 5. |
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Table 2. 81Br
nqcc's in CH81Br3 (MHz). Calculation
was made on the ro and rz structures. The subscripts in parentheses are the axes labels of
Ref. [1]. |
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Calc / ro |
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Calc / rz |
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Expt. [1] |
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Xuu(cc) |
- |
190.96 |
- |
196.19 |
- |
193.7768(40) |
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Xvv(aa) |
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454.69 |
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459.07 |
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454.3276(61) |
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Xww(bb) |
- |
263.74 |
- |
262.88 |
- |
260.5508(61) |
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Xuv(ac) |
- |
224.47 |
- |
216.14 |
- |
215.956(21) |
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RMS |
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2.46 (0.81 %) |
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3.35 (1.11 %) |
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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 |
- |
261.33 |
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261.06 |
- |
259.1432(122) |
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Xyy |
- |
263.74 |
- |
262.88 |
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260.5508(61) |
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Xzz |
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525.06 |
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523.94 |
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519.6940(129) |
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ETA |
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0.0046 |
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0.00349 |
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0.002709(26) |
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Øz,u |
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72.59 |
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73.293 |
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73.1598(13) |
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Øu,CBr |
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71.89 |
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72.378 |
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Øz,CBr |
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0.70 |
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0.915 |
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Table 3. Bromine
nqcc's in CH79Br281Br (MHz).
Calculation
was made on the ro and rz structures. The subscripts in parentheses are the axes labels of
Ref. [1]. |
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Calc / ro |
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Calc / rz |
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Expt. [1] |
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Xaa(79Br) |
- |
100.78 |
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- 98.70 |
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- 98.0355(54) |
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Xbb |
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329.26 |
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333.45 |
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329.9173(54) |
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Xcc |
- |
228.48 |
- |
234.74 |
- |
231.8817(27) |
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Xab |
± |
372.28 |
± |
374.11 |
± |
370.4827(51) |
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Xac |
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134.38 |
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129.40 |
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129.268(37) |
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Xbc |
± |
232.80 |
± |
224.16 |
± |
224.023(26) |
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RMS |
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2.56 (1.16 %) |
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2.65 (1.20 %) |
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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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Xaa(81Br) |
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454.84 |
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459.21 |
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454.4703(72) |
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Xbb |
- |
263.74 |
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262.88 |
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260.5589(72) |
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Xcc |
- |
191.10 |
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196.32 |
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193.9114(46) |
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Xac |
- |
224.26 |
- |
215.94 |
- |
215.775(56) |
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RMS |
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2.46 (0.81 %) |
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3.35 (1.11 %) |
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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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Table 4. Bromine
nqcc's in CH79Br81Br2 (MHz).
Calculation
was made on the ro and rz structures. The subscripts in parentheses are the axes labels of
Ref. [1]. |
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Calc / ro |
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Calc / rz |
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Expt. [1] |
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Xaa(79Br) |
- |
315.67 |
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314.66 |
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311.8953(64) |
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Xbb |
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544.06 |
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549.31 |
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543.6931(64) |
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Xcc |
- |
228.38 |
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234.66 |
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231.7977(46) |
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Xbc |
- |
268.93 |
- |
258.95 |
- |
258.891(36) |
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RMS |
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2.95 (0.81 %) |
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3.97 (1.10 %) |
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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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Xaa(81Br) |
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275.09 |
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278.58 |
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275.6192(59) |
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Xbb |
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- 84.06 |
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- 82.33 |
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- 81.7772(59) |
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Xcc |
- |
191.03 |
- |
196.26 |
- |
193.8420(25) |
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Xab |
± |
311.16 |
± |
312.68 |
± |
309.6045(49) |
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Xac |
± |
194.30 |
± |
187.08 |
± |
186.875(18) |
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Xbc |
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112.20 |
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108.03 |
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107.907(28) |
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RMS |
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2.11 (1.15 %) |
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2.23 (1.21 %) |
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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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| Table 5. Bromoform.
Structure parameters, rz [1] and ro [2]
(Å). |
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ro |
rz |
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CBr |
1.930(3) |
1.9260(3) |
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CH |
1.07(1) |
1.0831(32) |
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BrCBr |
110o48'(16') |
111.255(25)o |
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HCBr |
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107.622(27)o |
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| Table 6. CH79Br3.
Atomic coordinates, ro (top row) and rz
(bottom row). |
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u (Å) |
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v (Å) |
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w (Å) |
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Br |
- |
0.0356 |
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1.8344 |
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0.0 |
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- |
0.0347 |
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1.8356 |
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0.0 |
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Br |
- |
0.0356 |
- |
0.9172 |
± |
1.5886 |
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- |
0.0347 |
- |
0.9178 |
± |
1.5897 |
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C |
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0.5643 |
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0.0 |
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0.0 |
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0.5483 |
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0.0 |
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0.0 |
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H |
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1.6343 |
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0.0 |
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0.0 |
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1.6314 |
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0.0 |
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0.0 |
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[1] Z.Kisiel, A.Krasnicki,
L.Pszczółkowski, S.T.Shipman,
L.Alvarez-Valtierra, and B.H.Pate, J.Mol.Spectrosc. 257,177(2009): 63rd
OSU International Symposium on Molecular Spectroscopy, 2008, Abstract
WF09. |
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[2] Q.Williams, J.T.Cox, and W.Gordy,
J.Chem.Phys. 20,1524(1952). |
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CHCl3 |
CH3Br |
CH2Br2 |
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Table of Contents |
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Molecules/Bromine |
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CHBr3.html |
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Last
Modified 14 August 2009 |
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