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BrCH2-C(=O)Cl |
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Chlorine and Bromine |
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Nuclear
Quadrupole Coupling Constants |
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in Bromoacetyl Chloride |
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Chlorine and bromine nqcc's in bromoacetyl chloride have been determined by Merke et al. [1]. |
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Calculation was made here of
the nqcc's on a molecular structure given by PBE1PBE/6-31G(3d,3p)
optimization. These are compared with the experimental nqcc's in Tables 1 - 2. Structure parameters
are given in Table 3, rotational constants in Table 4.
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In Tables 1 - 2, the subscripts
a,b,c refer to the principal axes of the inertia tensor. Subscripts x,y,z refer to the principal axes of the nqcc tensor.
The nqcc y-axis is chosen coincident with the c-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
(percentage of average of absolute experimental nqcc's).
RSD
is the residual standard deviation of the calibration of the
computional model for calculation of the nqcc's. |
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Table 1. Chlorine nqcc's
in 79BrCH2CO35Cl (MHz). Calculation was made on the PBE1PBE/6-31G(3d,3p) optimized structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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46.58 |
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46.3386(31) |
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Xbb |
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23.34 |
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22.4542 |
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Xcc |
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23.24 |
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23.8844(25) |
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|Xab| |
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35.73 |
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35.287(35) |
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RMS |
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0.65 (2.1 %) |
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RSD |
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0.49 (1.1 %) |
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Xxx |
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38.37 |
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37.335(28) |
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Xyy |
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23.24 |
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23.8844(25) |
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Xzz |
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61.61 |
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61.220(29) |
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ETA |
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0.2457 |
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Øz,a |
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22.81 |
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22.866(15) |
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Øa,CCl |
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23.93 |
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24.283 * |
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Øz,CCl |
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1.12 |
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1.4 * |
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* Calculated in Ref. [1] on the molecular structure given by MP2/6-311++G(3df,2pd) optimization. |
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Table 2. Bromine nqcc's
in 79BrCH2CO35Cl (MHz). Calculation was made on the PBE1PBE/6-31G(3d,3p) optimized structure. |
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Calc. |
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Expt. [1] |
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79Br |
Xaa |
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506.58 |
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503.9195(17) |
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Xbb |
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202.29 |
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200.0205 |
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Xcc |
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304.30 |
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303.8990(16) |
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|Xab| |
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289.10 |
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291.454(13) |
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RMS |
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2.03 (0.60 %) |
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RSD |
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1.58 (0.39 %) |
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Xxx |
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305.24 |
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305.0281(99) |
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Xyy |
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304.30 |
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303.8990(16) |
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Xzz |
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609.54 |
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608.927(10) |
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ETA |
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0.001542 |
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Øz,a |
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19.60 |
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19.8135(68) |
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Øa,CBr |
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20.63 |
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20.517 * |
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Øz,CBr |
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1.03 |
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0.7 * |
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* Calculated in Ref. [1] on the molecular structure given by MP2/6-311++G(3df,2pd) optimization.
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Table 3. Structure parameters, PBE1PBE/6-31G(3d,3p) ropt in Z-matrix format (Å and degrees). |
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Br |
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C |
1 |
R1 |
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C |
2 |
R2 |
1 |
A1 |
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O |
3 |
R3 |
2 |
A2 |
1 |
D1 |
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Cl |
3 |
R4 |
2 |
A3 |
1 |
D2 |
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H |
2 |
R5 |
1 |
A4 |
3 |
D3 |
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H |
2 |
R5 |
1 |
A4 |
3 |
-D3 |
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R1 = 1.9066 |
A2 = 129.00 |
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R2 = 1.5028 |
A3 = 109.40 |
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R3 = 1.1780 |
A4 = 108.90 |
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R4 = 1.7876 |
D1 = 0.0 |
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R5 = 1.0908 |
D2 = 180. |
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A1 = 112.70 |
D3 = 120.97 |
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Note: Merke et al. report substitution coordinates for Cl and Br, from which I calculate Cl . . . Br = 4.4762 Å. The PBE1PBE structure gives Cl . . . Br = 4.4598 Å. |
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| Table 4. Rotational Constants, 79BrCH2CO35Cl (MHz). |
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Calc. ropt |
Expt. [1] |
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A |
9096.0 |
9029.45268(31) |
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B |
965.5 |
957.05898(35) |
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C |
877.7 |
870.04620(34) |
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[1] I.Merke, N.Vaeck, D.Petitprez, and G.Wlodarczak, J.Mol.Struct. 780-781,306(2006).
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CH3COCl |
HCOCl |
FCOCl |
FCH2COCl |
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CH3Br |
CH3CH2Br |
BrCH2COF |
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Table of Contents |
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Molecules/Chlorine |
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Molecules/Bromine |
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BrCH2COCl.html |
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Last
Modified 9 Sept 2005 |
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