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H2C=C=NH
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Nitrogen and Deuterium |
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Nuclear
Quadrupole Coupling Constants |
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in Ketenimine
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Calculation of the
nitrogen and deuterium nqcc's in ketenimine was made here on molecular
structures given by HF/ and MP2/aug-cc-pVTZ(G03) optimizations. These are
compared with the
experimental nqcc's [1] in Tables 1 and 2. Structure parameters are
given in Table 3, rotational constants in Table 4.
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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.
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 B3PW91/6-311+G(df,pd) and B3LYP/6-31G(df,3p) models respectively
for calculation of nitrogen and deuterium nqcc's. |
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Table 1. 14N nqcc's in Ketenimine (MHz). Calculation was made
on the (1) HF/aug-cc-pVTZ(G03) and (2) MP2/aug-cc-pVTZ(G03) 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 |
- |
0.151 |
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0.136 |
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0.030(46) |
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Xbb |
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1.526 |
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1.398 |
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1.523(40) |
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Xcc |
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1.375 |
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1.534 |
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1.553 |
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|Xac| |
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2.059 |
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1.950 |
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RMS |
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0.146 (14 %) |
0.095 (9.2 %) |
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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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1.385 |
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1.422 |
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Xyy |
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1.526 |
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1.398 |
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Xzz |
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2.911 |
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2.820 |
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ETA |
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0.048 |
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0.008 |
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Øz,a |
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126.72 |
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123.41 |
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Øa,NH |
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60.55 |
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59.39 |
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Øz,NH |
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66.16 |
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64.02 |
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Table 2. Deuterium nqcc's in N-Deuterated Ketenimine (kHz). Calculation was made
on the (1) HF/aug-cc-pVTZ(G03) and (2) MP2/aug-cc-pVTZ(G03) 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 |
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- 19.1 |
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- 10.2 |
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- 11(31) |
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Xbb |
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130.6 |
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118.4 |
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131(15) |
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Xcc |
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149.7 |
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128.7 |
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142 |
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|Xac| |
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181.2 |
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166.5 |
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RMS |
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14.9 (16 %) |
10.5 (11 %) |
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RSD |
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1.1 (0.86 %) |
1.1 (0.86 %) |
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Xxx |
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134.6 |
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121.2 |
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Xyy |
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130.6 |
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118.4 |
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Xzz |
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265.1 |
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239.6 |
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ETA |
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0.015 |
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0.011 |
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Øz,a |
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57.49 |
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56.32 |
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Øa,ND |
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59.06 |
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57.91 |
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Øz,ND |
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1.57 |
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1.59 |
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| Table 3. Ketenimine. Molecular structure parameters (Å
and degrees). |
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ropt (1) = HF/aug-cc-pVTZ(G03) optimization. |
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ropt (2) = MP2/aug-cc-pVTZ(G03) optimization. |
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ropt (1) |
ropt (2) |
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C=N |
1.2045 |
1.2290 |
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NH |
1.0024 |
1.0177 |
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CH |
1.0705 |
1.0781 |
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C=C |
1.2979 |
1.3143 |
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CNH |
115.56 |
115.54 |
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CCH |
119.91 |
119.77 |
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CCN |
176.05 |
173.76 |
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NCCH |
90.16 |
90.53 |
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| Table 4. Ketenimine. Rotational Constants (MHz). Normal Species. |
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ropt (1) = HF/aug-cc-pVTZ(G03) optimization. |
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ropt (2) = HF/aug-cc-pVTZ(G03) optimization. |
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Calc. ropt (1) |
Calc. ropt (2) |
Expt. [1] |
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A |
205 717.3 |
201 929.2 |
201 445.47(4) |
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B |
9 948.0 |
9 646.7 |
9 663.144(2) |
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C |
9 753.2 |
9 461.2 |
9 470.126(1) |
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[1] M.Rodler, R.D.Brown, P.D.Godfrey, and B.Kleibömer, J.Mol.Spectrosc. 118,267(1986).
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Methylenimine |
N-Methylacetamide |
N-Ethylformamide |
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Table of Contents |
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Molecules/Nitrogen |
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Molecules/Deuterium |
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H2CCNH.html |
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Last
Modified 30 Dec 2005 |
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