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HC=CC(=O)Cl |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in Propiolyl Chloride |
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Calculation was made of the Cl nqcc's in HCCC(=O)Cl and DCCC(=)OCl on the rz
molecular structure of Davis and Gerry [1], and on an approximate equilibrium ~re, given by MP2/aug-cc-pVTZ optimization with empirically corrected bond lengths. These are compared
with the experimental nqcc's [1] in Tables 1 and 2. Structure
parameters are given in Table 3. |
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In Tables 1 and 2, subscripts a,b,c refer to the
principal axes of the inertia tensor; x,y,z to the principal axes
of the nqcc tensor. The nqcc y-axis is chosen coincident with the
inertia c-axis, these are perpendicular to the molecular symmetry plane.
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 for the B1LYP/TZV(3df,2p) model
for calculation of the chlorine nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's. |
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Table 1. Chlorine
nqcc's in HCCC(=O)Cl (MHz). Calculation was made on rz [1] and ~re molecular structures. |
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Calc rz
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Calc ~re |
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Expt. [1] |
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Xaa(35Cl) |
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20.36 |
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20.10 |
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20.56(6) |
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Xbb |
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- 2.58 |
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- 2.77 |
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- 3.21(8) |
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Xcc |
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22.95 |
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22.86 |
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23.77(8) |
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|Xab| |
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52.27 |
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51.78 |
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RMS |
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0.61 (3.8 %) |
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0.64 (4.0 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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41.54 |
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41.06 |
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Xyy |
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22.95 |
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22.86 |
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Xzz |
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64.49 |
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63.93 |
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ETA |
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0.288 |
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0.285 |
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Øz,a |
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40.17 |
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40.25 |
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Øa,CCl |
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40.91 |
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41.11 |
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Øz,CCl |
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0.73 |
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0.86 |
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Xaa(37Cl) |
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17.50 |
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17.28 |
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16.80(12) |
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Xbb |
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- 0.59 |
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- 0.73 |
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- 1.68(13) |
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Xcc |
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18.08 |
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18.02 |
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18.48(13) |
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|Xab| |
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40.92 |
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40.54 |
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RMS |
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0.78 (6.3 %) |
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0.67 (4.2 %) |
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RSD |
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0.44 (1.1 %) |
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0.44 (1.1 %) |
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Table 2. Chlorine
nqcc's in DCCC(=O)Cl (MHz). Calculation was made on rz [1] and ~re molecular structures. |
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Calc rz
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Calc ~re |
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Expt. [1] |
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Xaa(35Cl) |
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16.40 |
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16.14 |
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16.43(15) |
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Xbb |
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- 6.54 |
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- 6.72 |
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- 7.20(18) |
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Xcc |
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22.95 |
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22.86 |
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23.63(18) |
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|Xab| |
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52.79 |
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52.28 |
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RMS |
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0.55 (3.5 %) |
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0.55 (3.5 %) |
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xaa(37Cl) |
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14.34 |
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14.13 |
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14.43(32) |
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Xbb |
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- 3.75 |
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- 3.89 |
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- 4.14(33) |
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Xcc |
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18.08 |
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18.02 |
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18.57(33) |
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|Xab| |
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41.45 |
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41.05 |
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RMS |
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0.36 (2.9 %) |
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0.39 (3.1 %) |
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RSD |
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0.44 (1.1 %) |
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0.44 (1.1 %) |
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| Table 3. HCCC(=O)Cl. Molecular structure parameters, rz
[1] and ~re (Å and degrees). Values in brackets are assumed. |
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rz |
~re |
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CH |
[1.055] |
1.0631 |
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C=C |
[1.207] |
1.1902 |
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CC |
1.4415 |
1.4358 |
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C=O |
1.1988(40) |
1.2048 |
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CCl |
1.7587(37) |
1.7685 |
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HC=C |
[180.0] |
179.80 |
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C=CC |
179.58(22) |
179.16 |
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CC=O |
125.19(30) |
126.40 |
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CCCl |
112.42(23) |
111.78 |
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[1] R.Wellington Davis
and M.C.L.Gerry, Can.J.Chem. 60,679(1982); R.Wellington Davis,
M.C.L.Gerry, S.Visaisouk, and W.J.Balfour, Chem.Phys.Lett. 26,561(1974). |
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O=CHCl |
O=CFCl |
O=CCl2 |
CH3C(=O)Cl |
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S=CCl2 |
S=CFCl |
s-t-CH2CHC(=O)Cl |
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Table of Contents |
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Molecules/Chlorine |
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HCCCOCl.html |
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Last
Modified 7 Dec 2008 |
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