CHBr3


 
 
 

 









Bromine


Nuclear Quadrupole Coupling Constants


in Bromoform


 








 


 




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].
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.
 
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.
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.

 








 






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].
 



Calc / ro Calc / rz
Expt. [1]




Xuu(cc) - 228.56 - 234.82 - 231.9631(33)
Xvv(aa) 544.23 549.48 543.8554(53)
Xww(bb) - 315.67 - 314.66 - 311.8922(53)
Xuv(ac) - 268.68 * - 258.70 * - 258.522(13)
 
RMS 2.94 (0.81 %) 3.98 (1.10 %)
RSD 1.58 (0.39 %) 1.58 (0.39 %)
 
Xxx - 312.79 - 312.49 - 310.2161(78)
Xyy - 315.67 - 314.66 - 311.8922(53)
Xzz 628.46 627.12 622.1083(87)
ETA 0.0046 0.00349 0.002694(15)
Øz,u 72.59 73.293 73.1593(7)
Øu,CBr 71.89 72.378
Øz,CBr   0.70   0.915
 


 







* The algebraic sign corresponds to the atomic coordinates given in Table 5.
 
 
 






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].
 



Calc / ro Calc / rz
Expt. [1]




Xuu(cc) - 190.96 - 196.19 - 193.7768(40)
Xvv(aa) 454.69 459.07 454.3276(61)
Xww(bb) - 263.74 - 262.88 - 260.5508(61)
Xuv(ac) - 224.47 - 216.14 - 215.956(21)
 
RMS 2.46 (0.81 %) 3.35 (1.11 %)
RSD 1.38 (0.40 %) 1.38 (0.40 %)
 
Xxx - 261.33 - 261.06 - 259.1432(122)
Xyy - 263.74 - 262.88 - 260.5508(61)
Xzz 525.06 523.94 519.6940(129)
ETA 0.0046 0.00349 0.002709(26)
Øz,u 72.59 73.293 73.1598(13)
Øu,CBr 71.89 72.378
Øz,CBr   0.70   0.915
 
 
 
 






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].
 



Calc / ro Calc / rz
Expt. [1]




Xaa(79Br) - 100.78 - 98.70 - 98.0355(54)
Xbb 329.26 333.45 329.9173(54)
Xcc - 228.48 - 234.74 - 231.8817(27)
Xab ± 372.28 ± 374.11 ± 370.4827(51)
Xac 134.38 129.40 129.268(37)
Xbc ± 232.80 ± 224.16 ± 224.023(26)
 
RMS 2.56 (1.16 %) 2.65 (1.20 %)
RSD 1.58 (0.39 %) 1.58 (0.39 %)
 
Xaa(81Br) 454.84 459.21 454.4703(72)
Xbb - 263.74 - 262.88 - 260.5589(72)
Xcc - 191.10 - 196.32 - 193.9114(46)
Xac - 224.26 - 215.94 - 215.775(56)
 
RMS 2.46 (0.81 %) 3.35 (1.11 %)
RSD 1.38 (0.40 %) 1.38 (0.40 %)
 
 
 
 






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].
 



Calc / ro Calc / rz
Expt. [1]




Xaa(79Br) - 315.67 - 314.66 - 311.8953(64)
Xbb 544.06 549.31 543.6931(64)
Xcc - 228.38 - 234.66 - 231.7977(46)
Xbc - 268.93 - 258.95 - 258.891(36)
 
RMS 2.95 (0.81 %) 3.97 (1.10 %)
RSD 1.58 (0.39 %) 1.58 (0.39 %)
 
Xaa(81Br) 275.09 278.58 275.6192(59)
Xbb - 84.06 - 82.33 - 81.7772(59)
Xcc - 191.03 - 196.26 - 193.8420(25)
Xab ± 311.16 ± 312.68 ± 309.6045(49)
Xac ± 194.30 ± 187.08 ± 186.875(18)
Xbc 112.20 108.03 107.907(28)
 
RMS 2.11 (1.15 %) 2.23 (1.21 %)
RSD 1.38 (0.40 %) 1.38 (0.40 %)
 
 
 
Table 5.  Bromoform.  Structure parameters, rz [1] and ro [2] (Å).
 
   ro    rz
CBr 1.930(3) 1.9260(3)
CH 1.07(1) 1.0831(32)
BrCBr 110o48'(16') 111.255(25)o
HCBr 107.622(27)o
 
Table 6.  CH79Br3.  Atomic coordinates, ro (top row) and rz (bottom row).
 
  u (Å)   v (Å)   w (Å)
Br - 0.0356 1.8344 0.0
- 0.0347 1.8356 0.0
Br - 0.0356 - 0.9172 ± 1.5886
- 0.0347 - 0.9178 ± 1.5897
C 0.5643 0.0 0.0
0.5483 0.0 0.0
H 1.6343 0.0 0.0
1.6314 0.0 0.0
 
 

[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.
[2] Q.Williams, J.T.Cox, and W.Gordy, J.Chem.Phys. 20,1524(1952).
 
 

CHCl3 CH3Br CH2Br2

 








 








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Molecules/Bromine

 








 













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Last Modified 14 August 2009