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NH2-C(=O)-CH2Cl
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Nitrogen and Chlorine |
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Nuclear
Quadrupole Coupling Constants |
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in 2-Chloroacetamide
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"Rough values of the chlorine
nuclear quadrupole coupling constants" in 2-chloroacetamide were
derived by Møllendal and Samdal [1]. |
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Calculation of the
nitrogen and chlorine nqcc's in 2-chloroacetamide was made here on molecular
structures given by HF/6-311++G(3df,3pd) optimization (see acetamide),
and by B3LYP/6-311++G(3df,2pd) optimization [1]. Calculated
nitrogen nqcc's are shown in Table 1. Calculated chlorine nqcc's
are
compared with the experimental values [1] in Tables 2 and 3.
Structure parameters are
given in Table 4, rotational constants in Table 5.
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In Tables 1 - 3, 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 nqcc's (percentage of the
average of the magnitudes of the experimental nqcc's). RSD is the
calibration residual standard deviation of the model for calculation of the nqcc's. |
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Table 1. 14N nqcc's in 2-Chloroacetamide-35Cl (MHz). Calculation was made
on the (1) HF/6-311++G(3df,3pd) and (2) B3LYP/6-311++G(3df,2pd) optimized structures. |
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Calc. (1)
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Calc. (2) |
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Expt. |
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Xaa |
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1.711 |
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1.728 |
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Xbb |
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2.023 |
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2.057 |
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Xcc |
- |
3.734 |
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3.785 |
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|Xab| |
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0.145 |
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0.130 |
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RSD |
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0.030 (1.3 %) |
0.030 (1.3 %) |
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Xxx |
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1.654 |
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1.683 |
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Xyy |
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2.080 |
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2.102 |
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Xzz |
- |
3.734 |
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3.785 |
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ETA |
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0.114 |
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0.111 |
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Table 2. 35Cl nqcc's in 2-Chloroacetamide (MHz). Calculation was made
on the (1) HF/6-311++G(3df,3pd) and (2) B3LYP/6-311++G(3df,2pd) optimized structures. |
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Calc. (1)
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Calc. (2) |
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Expt. [1] |
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Xaa |
- |
44.81 |
- |
45.35 |
- |
47.62(52) |
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Xbb |
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6.67 |
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7.04 |
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8.22(66) |
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Xcc |
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38.14 |
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38.30 |
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39.40 * |
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|Xab| |
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45.64 |
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45.36 |
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RMS |
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1.99 (6.2 %) |
1.61 (5.1 %) |
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RSD |
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0.49 (1.1 %) |
0.49 (1.1 %) |
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Xxx |
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33.33 |
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33.22 |
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Xyy |
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38.14 |
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38.30 |
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Xzz |
- |
71.47 |
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71.53 |
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ETA |
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0.067 |
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0.071 |
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Øa,z |
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30.29 |
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30.00 |
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Øa,CCl |
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30.36 |
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30.20 |
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Øz,CCl |
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0.07 |
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0.21 |
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* Calculated here from zero trace condition. |
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Table 3. 37Cl nqcc's in 2-Chloroacetamide (MHz). Calculation was made
on the (1) HF/6-311++G(3df,3pd) and (2) B3LYP/6-311++G(3df,2pd) optimized structures. |
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Calc. (1)
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Calc. (2) |
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Expt. [1] |
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Xaa |
- |
35.38 |
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35.80 |
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34.6(10) |
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Xbb |
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5.32 |
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5.61 |
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6.2(11) |
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Xcc |
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30.06 |
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30.19 |
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28.4 * |
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|Xab| |
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35.93 |
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35.71 |
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RMS |
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1.2 (5.1 %) |
1.3 (5.6 %) |
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RSD |
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0.44 (1.1 %) |
0.44 (1.1 %) |
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Xxx |
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26.27 |
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26.18 |
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Xyy |
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30.06 |
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30.19 |
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Xzz |
- |
56.32 |
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56.37 |
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ETA |
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0.067 |
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0.071 |
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Øa,z |
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30.24 |
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39.95 |
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Øa,CCl |
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30.31 |
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30.16 |
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Øz,CCl |
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0.07 |
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0.21 |
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* Calculated here from zero trace condition. |
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| Table 4. 2-Chloroacetamide. Molecular structure parameters (Å
and degrees). HF and B3LYP optimizations with MP2/6-311+G(2d,p) correction for CCl bond length [2]. PDF |
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ropt (1) = HF/6-311++G(3df,3pd) optimization. |
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ropt (2) = B3LYP/6-311++G(3df,2pd) optimization. |
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| Point Group: Cs |
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ropt (1) |
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ropt (2) |
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ClC(2) |
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1.7804 |
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1.7804 |
| C(2)C(3) |
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1.5209 |
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1.5256 |
| C(2)H(8,9) |
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1.0756 |
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1.0853 |
| C(3)O |
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1.1920 |
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1.2154 |
| C(3)N |
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1.3381 |
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1.3485 |
| NH(6) |
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0.9911 |
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1.0055 |
| NH(7) |
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0.9884 |
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1.0049 |
| Cl - - - H(7) |
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2.5337 |
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2.5051 |
| ClC(2)C(3) |
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116.78 |
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116.72 |
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ClC(2)H(8,9) |
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107.64 |
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107.21 |
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C(2)C(3)O |
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117.20 |
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117.49 |
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C(2)C(3)N |
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118.92 |
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118.13 |
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C(3)NH(6) |
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117.93 |
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118.45 |
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C(3)NH(7) |
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122.25 |
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121.53 |
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C(3)ClC(2)H(8,9) |
± |
121.22 |
± |
121.48 |
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| Table 5. 2-Chloroacetamide. Rotational Constants (MHz). 35Cl Species. |
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ropt (1) = HF/6-311++G(3df,3pd) optimization. |
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ropt (2) = B3LYP/6-311++G(3df,2pd) optimization. |
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Calc. ropt (1) |
Calc. ropt (2) |
Expt. [1] |
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A |
9824.7 |
9693.7 |
9640.4724(87) |
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B |
2410.4 |
2394.4 |
2402.1687(15) |
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C |
1958.8 |
1943.4 |
1948.3733(15) |
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[1]
H.Møllendal and S.Samdal, J.Phys.Chem. A 110,2139(2006); PRAHA2006: The 19th International Conference
on High Resolution Molecular Spectroscopy, Abstract L12.
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[2] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).
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Acetamide |
alpha-Fluoroacetamide |
N-Methylacetamide |
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Table of Contents |
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Molecules/Nitrogen |
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Molecules/Chlorine |
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2ClAcetamide.html |
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Last
Modified 27 July 2006 |
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