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O=C=C(H)CN
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Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in Cyanoketene |
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Nitrogen nqcc's in cyanoketene a mixed rs/ro
structure was reported by Hahn, et al. [1]. Calculation
of the nqcc's was made on this structure, and on an approximate re structure given by MP2/aug-cc-pVTZ optimization with empirically corrected bond lengths. These calculated nqcc's are
compared with the experimental values in Table 1. Structure parameters
are given in Table 2. |
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In Table 1, subscripts a,b,c refer to the principal axes of the inertia
tensor, subscripts 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 plane of the molecule. 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 nqcc's (percentage of
average experimental nqcc). RSD is the residual stand deviation
of calibration of the B3PW91/6-311+G(df,pd) model for calculation of
the nqcc's. |
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Table 1. 14N nqcc's
in Cyanoketene (MHz). Calculation was made on the rs/ro and approximate re structures.
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Calc / rs/ro |
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Calc / re |
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Expt. [1] |
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Xaa |
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2.437 |
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2.465
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2.461(13) |
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Xbb |
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1.290 |
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1.316
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1.220(12) |
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Xcc |
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1.147 |
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1.149
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1.241(18) |
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|Xab| |
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2.937 |
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2.921
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RMS |
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0.069 (4.2 %) |
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0.077 (4.7 %)
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RSD |
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xxx |
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2.905 |
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2.905
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2.709(44) * |
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Xyy |
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1.147 |
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1.149
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1.241(18) |
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Xzz |
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4.052 |
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4.054
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3.950(82) |
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ETA |
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0.434 |
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0.433
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0.372(15) |
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Øz,a |
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28.80 |
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28.54
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Øa,CN |
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28.14 |
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28.32
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28.22 |
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Øz,CN |
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0.66 |
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0.22
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* Bond axis nqcc's on rs/ro structure [1].
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| Table 2. Structure
parameters, rs/ro [1] and approximate re (Å and degrees). |
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rs/ro |
re |
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NC |
1.158(1) | 1.1581
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C-C |
1.434(6) | 1.4174
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CH |
1.059(34) | 1.0791
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C=C |
1.334(12) | 1.3261
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OC |
1.148(8) | 1.1505
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NC-C |
178.1(5) | 178.85
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HC=C |
119.9(2) | 117.70
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C=C-C |
118.5(12) | 120.54
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O=C=C |
176.5(15) | 179.02
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[1] M.Hahn, H.-K.Bodenseh, and M.Ferner, J.Mol.Spectrosc.
223,138(2004). |
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Ketene |
Chloroketene |
Bromoketene |
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Table of Contents |
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Molecules/Nitrogen |
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CNketene.html |
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Last
Modified 9 Dec 2011 |
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