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CH2CHCH=NH |
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Nitrogen
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Nuclear
Quadrupole Coupling Constants |
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in trans-anti-Propenimine |
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14N
nqcc's in trans-anti-propenimine were determined by Krause and Sutter [1]. Earlier
measurements had been made by Brown et al. [2]. A partial substitution
structure was proposed by Penn [3]. Calculation of the nqcc's was
made here on this structure. The results are compared with the experimental
nqcc's in Table 1. |
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Calculation was made also on B3P86/ and
MP2/6-311+G(3d,3p) optimized molecular structures. These nqcc's are
compared with the experimental values in Table 2. Structure parameters
are compared in Table 3, rotational constants in Table 4. |
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In Tables 1 and 2, 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) model
for calculation of the nitrogen nqcc's. |
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Subscripts a,b,c refer to the
principal axes of the inertia tensor; 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 molecular symmetry plane.
Ø (degrees) is the angle between its subscripted
parameters. ETA = (Xxx - Xyy)/Xzz. |
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Table 1. Nitrogen nqcc's in trans-anti-CH2=CHCH=NH (MHz). Calculation was made
on the partial substitution structure of Penn [3]. |
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Calc. |
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Expt. [1] |
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14N |
Xaa |
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0.819 |
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0.7414(11) |
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Xbb |
- |
4.087 |
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3.8461(11) |
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Xcc |
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3.268 |
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3.1047(16) |
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|Xab| |
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1.227 |
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RMS |
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0.174 (6.8 %) |
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RSD |
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0.030 (1.3 %) |
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Table 2. 14N nqcc's in trans-anti-CH2=CHCH=NH (MHz). Calculation was made on the B3P86/ and MP2/6-311+G(3d,3p) optimized structures. |
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Calc/B3P86
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Calc/MP2 |
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Expt. [1] |
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Xaa |
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0.758 |
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0.768 |
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0.7414(11) |
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Xbb |
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3.872 |
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3.834 |
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3.8461(11) |
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Xcc |
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3.114 |
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3.066 |
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3.1047(16) |
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|Xab| |
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1.185 |
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1.123 |
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RMS |
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0.019 (0.73 %) |
0.028 (1.1 %) |
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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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1.043 |
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1.028 |
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Xyy |
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3.114 |
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3.066 |
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Xzz |
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4.158 |
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4.094 |
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ETA |
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0.498 |
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0.498 |
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Øz,b |
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76.44 |
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76.99 |
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Øb,bi |
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81.24 |
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80.96 |
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Øz,bi * |
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4.80
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2.97 |
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* Angle between the z-axis and the bisector ('bi') of the CNH angle. |
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| Table 3. Molecular structure parameters, partial rs [3], and B3P86 and MP2/6-311+G(3d,3p) (Å
and degrees). |
| Hc and Ht are
with respect to the imine H. * Assumed value. |
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rs [3] |
B3P86 |
MP2 |
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NH |
1.014 |
1.0182 |
1.0197 |
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C(1)N |
1.274 |
1.2720 |
1.2856 |
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C(1)C(2) |
1.454(2) |
1.4561 |
1.4611 |
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C(2)C(3) |
1.336(2) |
1.3316 |
1.3423 |
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C(1)H |
1.086 * |
1.0970 |
1.0941 |
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C(2)H |
1.086 * |
1.0843 |
1.0829 |
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C(3)Hc |
1.086 * |
1.0841 |
1.0826 |
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C(3)Ht |
1.086 * |
1.0814 |
1.0800 |
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HNC(1) |
111.7 |
110.74 |
109.89 |
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NC(1)C(2) |
121.5 |
121.17 |
120.68 |
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C(1)C(2)C(3) |
122.9(2) |
122.46 |
122.15 |
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C(2)C(1)H |
120 * |
115.52 |
116.13 |
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C(1)C(2)H |
120 * |
115.91 |
116.30 |
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C(2)C(3)Hc |
120 * |
121.13 |
120.82 |
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C(2)C(3)Ht |
120 * |
121.84 |
121.67 |
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| Table 4. Rotational Constants (MHz). |
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B2P86 opt |
MP2 opt |
Expt. [2] |
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A |
46 672 |
45 095 |
45 773.628(18) |
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B |
4596.4 |
4555.0 |
4560.916(4) |
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C |
4184.3 |
4145.4 |
4148.242(3) |
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[1] H.Krause and
D.H.Sutter, Z.Naturforsch. 46a,785(1991). |
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[2] R.D.Brown, P.D.Godfrey, and D.A.Winkler,
Chem.Phys. 59,243(1981). |
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[3] R.E.Penn, J.Mol.Spectrosc.
69,373(1978). |
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CH2NH |
CF2NH |
Ethylenimine |
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cis-Ethanimine |
trans-Ethanimine |
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trans-syn-Propenimine |
(CH3)2NH |
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Table of Contents |
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Molecules/Nitrogen |
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TAPropenimine.html |
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Last
Modified 24 Feb 2005 |
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