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CH2Cl |
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in the Chloromethyl Radical |
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Calculation was made of the Cl nqcc
tensors in the chloromethyl radical on a structure given by MP2/aug-cc-pVTZ optimization (assuming C2V symmetry), ropt; and on this structure but with empirically corrected CCl bond length, ~re. These are compared with the experimental
nqcc's of Bailleux [1] in Table 1. Structure
parameters are given in Table 2, rotational constants in Table 3. |
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In Table 1, subscripts a,b,c refer to the
principal axes of the inertia tensor. ETA = (Xbb - Xcc)/Xaa = (Xxx - Xyy)/Xzz, where x,y,z are principal axes
of the nqcc tensor. |
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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 CH2Cl Radical (MHz). Calculation was made on the ropt and ~re structures. |
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Calc. ropt |
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Calc. ~re |
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Expt. [1] |
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Xaa(35Cl) |
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65.74 |
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65.50 |
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66.0697(77) |
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Xbb - Xcc |
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19.80 |
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19.95 |
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19.567(164) |
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Xbb |
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42.77 |
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42.73 |
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42.818 * |
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Xcc |
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22.97 |
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22.78 |
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23.251 * |
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ETA |
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0.301 |
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0.304 |
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RMS |
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0.25 (0.57 %) |
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0.43 (0.97 %) |
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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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51.81 |
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51.62 |
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52.3928(140) |
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Xbb - Xcc |
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15.60 |
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15.72 |
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16.467(236) |
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Xbb |
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33.71 |
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33.68 |
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34.430 * |
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Xcc |
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18.10 |
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17.95 |
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17.963 * |
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ETA |
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0.301 |
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0.304 |
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RMS |
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0.54 (1.6 %) |
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0.62 (1.8 %) |
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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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* Calculated here from experimental Xaa (= - Xbb - Xcc) and Xbb - Xcc. |
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| Table 2. Chloromethyl Radical. Molecular structure parameters (Å and degrees). |
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ropt |
~re |
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HC |
1.0730 |
1.0730 |
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CCl |
1.6932 |
1.6901 |
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HCCl |
117.84 |
117.84 |
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| Table 3. Chloromethyl Radical. Rotational Constants (MHz). 35Cl species. |
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ropt |
~re |
Expt. [1] |
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A |
278 470.1 |
278 470.1 |
274 317.60(52) |
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B |
15 987.1 |
16 042.8 |
15 948.00830(79) |
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C |
15 119.1 |
15 168.9 |
15 057.06934(79) |
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[1] S.Bailleux, P.Dréan, Z.Zelinger, M.Godon, J.Mol.Spectrosc. 229,140(2005). |
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CCl |
NCl |
OCl |
SiCl |
ClOO |
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Table of Contents |
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Molecules/Chlorine |
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CH2Cl.html |
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Last
Modified 22 Dec 08 |
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