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H2C=CH-AsH2
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Arsenic |
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Nuclear
Quadrupole Coupling Constants |
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in
Vinylarsine
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Arsenic nqcc's in the two conformers
of vinylarsine shown below were determined by Dréan et al. [1].
An equilibrium structure of the syn
conformer was derived by Demaison et al. [2]. |
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Calculation of the nqcc tensors was
made here on molecular
structures given by MP2/6-311++G(3df,3pd) optimizations and, for
the syn conformer, the re structure of Demaison et al.
These are compared with the experimental nqcc's in the syn form in Table 1, and in the gauche form in Table 2.
Molecular structure parameters are given here in Z-matrix format. Rotational
constants are given in Table 3.
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Syn (CS) |
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Gauche (C1)
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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 PBE1PBE/6-311++G(3df,3pd) model for calculation of the nqcc's. |
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Table 1. 75As nqcc's in syn-Vinylarsine (MHz).
Calculation was made on the MP2/6-311++G(3df,3pd) optimized
structure, and on the re structure. |
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Calc/MP2 |
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Calc/re |
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Expt. [1] |
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Xaa |
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93.4 |
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91.5 |
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88.1053(67) |
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Xbb |
- |
174.5 |
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173.0 |
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165.401(76) |
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Xcc |
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81.0 |
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81.5 |
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77.299(10) |
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|Xab| |
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47.9 |
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49.2 |
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RMS |
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6.4 (5.8 %) |
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5.4 (4.9 %) |
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RSD |
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3.5 (2.8 %) |
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3.5 (2.8 %) |
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Xxx |
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101.7 |
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100.3 |
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Xyy |
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81.0 |
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81.5 |
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Xzz |
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182.8 |
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181.8 |
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ETA |
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0.113 |
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0.103 |
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Table 2. Arsenic nqcc's
in gauche-Vinylarsine
(MHz). Calculation was made on the MP2/6-311++G(3df,3pd)
optimized structure. |
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Calc. |
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Expt. [1] |
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75As |
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Xaa |
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2.2 |
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- 3.96(40) |
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Xbb |
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73.9 |
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74.896(53) |
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Xcc |
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- 76.2 |
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70.94(47) |
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|Xab| |
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54.9 |
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|Xac| |
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123.8 |
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|Xbc| |
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48.0 |
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RMS |
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4.7 (9.4 %) |
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RSD |
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3.5 (2.8 %) |
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Xxx |
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108.5 |
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Xyy |
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77.8 |
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Xzz |
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186.3 |
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ETA |
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0.165 |
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Molecular Structures: See Z-Matrix.
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| Table 3. Vinylarsine
MP2/6-311++G(3df,3pd) Structures. Rotational
Constants (MHz). Normal Species. |
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Calc. |
Expt. [1] |
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syn |
A |
36 659.1 |
36 322.959(29) |
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B |
3 936.2 |
3 941.36086(89) |
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C |
3 678.6 |
3 678.56301(99) |
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gauche |
A |
37 658.7 |
37 441.408(37) |
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B |
3 854.7 |
3 848.7989(14) |
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C |
3 604.4 |
3.597.7834 |
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[1]
P.Dréan, D.Petitprez, J.Demaison, J.C.López, J.L.Alonso,
J.-C.Guillemin, and J.E.Boggs, J.Mol.Spectrosc. 190,365(1998). |
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[2] J.Demaison, H.Møllendal,
and J.-C.Guillemin, J.Mol.Struct. 930,21(2009). |
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AsCl3
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AsD3 |
AsH2 |
AsP |
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Table of Contents |
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Molecules/Arsenic |
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CH2CHAsH2.html |
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Last
Modified 2 Oct 2009 |
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