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t-HCCCH2-CH2Cl
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Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in trans-Chlorobutyne
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Calculation of the chlorine nqcc's in t-chlorobutyne
was made on a structure given by MP2/aug-cc-pVTZ(G03) optimization with empirical correction for the CCl, C-C, and the acetylenic CC bond lengths (~ re).
These are compared with the experimental nqcc's of Keske et al.
[1] in Tables 1 - 2. Structure parameters are given in
Table 3; rotational constants in Table 4. |
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In Tables 1 - 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. 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 inertial axes nqcc's.
RSD is the calibration residual standard deviation of
the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's. |
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Table 1. Chlorine
nqcc's in t-chlorobutyne (MHz). Calculation was made on the ~ re structure. |
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Calc. |
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Expt. [1] |
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35Cl |
Xaa |
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60.57 |
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59.843(3) |
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Xbb - Xcc |
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12.44 |
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12.550(6) |
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Xbb |
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24.06 |
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23.6465 * |
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Xcc |
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36.51 |
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36.1965 * |
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|Xab| |
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32.91 |
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33.7(6) |
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RMS |
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0.52 (1.3 %) |
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RSD |
0.49 (1.1 %) |
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Xxx |
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35.35 |
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35.55 ** |
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Xyy |
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36.51 |
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36.1965 |
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Xzz |
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71.86 |
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71.75 |
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ETA |
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0.016 |
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0.009 |
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Øz,a |
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18.93 |
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19.46 |
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Øa,CCl |
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18.29 |
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Øz,CCl |
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0.64 |
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* Calculated here from experimental Xaa and Xbb - Xcc. ** Calculated here from the experimental data using Z. Kisiel's QDIAG.f. See http://info.ifpan.edu.pl/~kisiel/prospe.htm
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Table 2. Chlorine
nqcc's in t-chlorobutyne (MHz). Calculation was made on the ~ re structure. |
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Calc. |
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Expt. [1] |
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37Cl |
Xaa |
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47.74 |
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47.174(3) |
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Xbb - Xcc |
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- 9.80 |
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- 9.885(8) |
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Xbb |
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18.97 |
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18.6445 * |
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Xcc |
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28.77 |
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28.5295 * |
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|Xab| |
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25.93 |
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26.6(6) |
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RMS |
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0.40 (1.3 %) |
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RSD |
0.44 (1.1 %) |
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Xxx |
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27.86 |
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28.05 |
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Xyy |
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28.77 |
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28.5295 |
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Xzz |
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56.63 |
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56.58 |
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ETA |
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0.016 |
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0.008 |
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Øz,a |
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18.93 |
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19.47 |
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Øa,CCl |
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18.29 |
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Øz,CCl |
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0.64 |
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* Calculated here from experimental Xaa and Xbb - Xcc. ** Calculated here from the experimental data using Z. Kisiel's QDIAG.f. See http://info.ifpan.edu.pl/~kisiel/prospe.htm |
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| Table 3. t-Chlorobutyne (Cs). Selected structure parameters, ~ re (Å
and degrees). Complete structure is given here in Z-matrix format. |
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ClC(2) |
1.7826 |
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| C(2)C(3) |
1.5203 |
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| C(3)C(8) |
1.4597 |
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| C(8)C(9) |
1.2047 |
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| C(9)H(10) |
1.0620 |
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| ClC(2)C(3) |
110.15 |
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| C(2)C(3)C(8) |
109.98 |
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| C(3)C(8)C(9) |
177.47 |
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| C(8)C(9)H(10) |
179.06 |
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| Click on image to enlarge. |
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| Table 4. t-Chlorobutyne. Rotational constants, 35Cl species (MHz). |
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~ re |
expt. [1] |
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A |
26 406.1 |
26 349.1595(15) |
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B + C |
2 963.9 |
2 938.3634(3) |
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B - C |
55.8 |
54.9262(6) |
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[1] J.C.Keske,
F.S.Rees, R.D.Suenram, and B.H.Pate, PCCP 5,1599(2003). The
experimental nqcc's and rotational constants given above were obtained
from B.H.Pate via personal communication. These differ
slightly from those published in this paper. |
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gauche-HCCCH2-CH2Cl |
Chloroethanes
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Table of Contents |
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Molecules/Chlorine |
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tHCCCH2CH2Cl.html |
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Last
Modified 8 Feb 2008 |
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