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Si(H)SiH
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Deuterium |
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Nuclear
Quadrupole Coupling Constants |
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in Monobridged Disilyene
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Calculation of deuterium nqcc's in Si(D)SiH and Si(H)SiD were made here on (1) the ro molecular
structure of McCarthy and Thaddeus [1], (2) the partial ro structure of Cordonnier et al. [2], and (3) a structure optained by MP2/aug-cc-pVTZ(G03) optimization (assuming Cs symmetry). These are
compared with the
experimental nqcc's [1] in Tables 1 and 2. Structure parameters are
given in Table 3.
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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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RSD is the calibration residual standard deviation of
the B3LYP/6-31G(df,3p) model
for calculation of the deuterium nqcc's, which may be taken as an estimate of the uncertainty in the calculated nqcc's. |
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Table 1. Deuterium nqcc's in Si(D)SiH (kHz). Calculation was made
on (1) the ro molecular
structure of McCarthy and Thaddeus [1], on (2) the partial ro molecular
structure of Cordonnier et al. [2], and on (3) the MP2/aug-cc-pVTZ structure. |
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Calc. (1)
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Calc. (2) |
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Calc. (3) |
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Expt. [1] |
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Xaa |
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34.2 |
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29.5 |
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30.0 |
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31(1) |
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Xbb |
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34.6 |
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31.7 |
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31.3 |
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Xcc |
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68.8 |
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61.2 |
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61.4 |
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|Xab| |
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15.0 |
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8.2 |
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5.5 |
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RSD |
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1.1 (0.86 %) |
1.1 (0.86 %) |
1.1 (0.86 %) |
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Xxx |
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19.4 |
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22.3 |
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25.1 |
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Xyy |
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49.4 |
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38.9 |
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36.2 |
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Xzz |
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68.8 * |
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61.2 * |
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61.4 * |
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ETA |
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0.435 |
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0.270 |
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0.181 |
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* The z-principal axis is perpendicular to the ab-plane of the molecule. |
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Table 2. Deuterium nqcc's in Si(H)SiD (kHz). Calculation was made
on (1) the ro molecular
structure of McCarthy and Thaddeus [1], on (2) the partial ro molecular
structure of Cordonnier et al. [2], and on (3) the MP2/aug-cc-pVTZ structure. |
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Calc. (1)
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Calc. (2) |
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Calc. (3) |
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Expt. [1] |
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Xaa |
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68.3 |
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82.9 |
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81.2 |
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79(1) |
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Xbb |
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22.2 |
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29.8 |
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30.4 |
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Xcc |
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46.1 |
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53.1 |
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50.8 |
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|Xab| |
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42.8 |
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43.8 |
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38.1 |
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RSD |
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1.1 (0.86 %) |
1.1 (0.86 %) |
1.1 (0.86 %) |
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Xxx |
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39.2 |
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44.8 |
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42.2 |
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Xyy |
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46.1 |
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53.1 |
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50.8 |
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Xzz |
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85.3 |
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98.0 |
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93.0 |
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ETA |
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0.081 |
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0.085 |
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0.092 |
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Øz,a |
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21.7 |
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18.9 |
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17.16 |
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Øa,SiD |
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23.6 |
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20.4 |
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18.45 |
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Øz,SiD |
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1.9 |
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1.5 |
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1.29 |
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| Table 3. Monobridged Disilyene. Molecular structure parameters, ro [1,2], and ropt = MP2/aug-cc-pVTZ(G03) (Å
and degrees). |
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| Click on image |
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ro [1] |
ro [2] |
ropt |
| to enlarge. |
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SiSi |
2.119(1) |
2.119 |
2.1291 |
| Si(2)H(3) |
1.586(19) |
1.629 |
1.6356 |
| Si(2)H(4) |
1.506(4) |
1.474 |
1.4851 |
| SiSiH(3) |
52.2(8) |
52.5 (fixed) |
51.91 |
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SiSiH(4) |
153.9(4) |
157.5 |
159.65 |
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[1] M.C.McCarthy and P.Thaddeus, J.Mol.Spectrosc. 222,248(2003). |
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[2] M.Cordonnier, M.Bogey, C.Demuynck, and J.-L.Destombes, J.Chem.Phys. 97,7984(1992).
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Table of Contents |
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Molecules/Deuterium |
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SiHSiH.html |
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Last
Modified 1 Jan 2009 |
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