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1. Heteropolar double bonds |
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21 |
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TABLE 9. CAS(4,4)/CEP-DZP energies of CH(A)DXH2 and CH2DXH(A) |
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X |
A |
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CH(A)DXH2 |
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CH2DXH(A) |
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Conformationa |
Energy |
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Conformation |
Energy |
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A |
Total |
(a.u.) |
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A |
Total |
(a.u.) |
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C |
CH3 |
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T |
P |
19.974071 |
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18.206471 |
Si |
CH3 |
|
T |
P |
18.194894 |
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T |
P |
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Ge |
CH3 |
|
T |
P |
18.148716 |
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T |
P |
18.156259 |
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Sn |
CH3 |
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T |
P |
17.702732 |
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T |
P |
17.707825 |
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Pb |
CH3 |
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T |
TB |
17.754138 |
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T |
P |
17.766754 |
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C |
F |
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P |
36.597301 |
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Si |
F |
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P |
34.808242 |
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P |
34.886244 |
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Ge |
F |
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TB |
34.762843 |
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P |
34.816868 |
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TB |
34.816562 |
Sn |
F |
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TB |
34.320467 |
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P |
34.373884 |
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Pb |
F |
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TB |
34.370934 |
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TB |
34.371716 |
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TB |
34.428810 |
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C |
OH |
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C |
P |
29.009014 |
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27.285140 |
Si |
OH |
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T |
P |
27.221906 |
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T |
P |
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Ge |
OH |
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C |
TB |
27.177137 |
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T |
P |
27.216579 |
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Sn |
OH |
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T |
TB |
26.737427 |
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T |
TB |
26.767659 |
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Pb |
OH |
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T |
TB |
27.791738 |
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T |
TB |
26.821687 |
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C |
CN |
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P |
27.897308 |
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Si |
CN |
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P |
26.124578 |
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P |
26.134046 |
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Ge |
CN |
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P |
26.078417 |
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P |
26.082600 |
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Sn |
CN |
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P |
25.634561 |
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TB |
25.641678 |
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Pb |
CN |
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TB |
25.683015 |
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TB |
25.697117 |
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C |
NO |
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C |
P |
38.027269 |
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36.247614 |
Si |
NO |
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C |
P |
36.250112 |
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C |
P |
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Ge |
NO |
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C |
P |
36.206408 |
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C |
P |
36.196001 |
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Sn |
NO |
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C |
P |
35.762685 |
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C |
TB |
35.747911 |
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Pb |
NO |
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C |
P |
35.813392 |
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C |
TB |
35.813049 |
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a C D cis, T D trans, P D planar, TB D trans-bent. Conformation of A is with regard to the local carbene geometry.
the less stable isomer correlates with the higher combined carbene fragment S T splitting energy. The electronic structure factors that make the CN substituent different must now be sought.
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