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[[VBTutorial4| return to Tutorial n°4]] | [[VBTutorial4| return to Tutorial n°4]] | ||
| − | + | Two geometries are provided the planar and the twisted where a vinyl part C1 C5 has been twisted by 90°. | |
| − | == | + | this second moieties has its pi orbitals along the y direction. |
| + | ==Evaluation of the conjugaison== | ||
| + | {| class="collapsible collapsed wikitable" | ||
| + | |- | ||
| + | !'''Planar geometry''' | ||
| + | |- | ||
| + | | | ||
<html><pre> | <html><pre> | ||
$contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end | $contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end | ||
$SYSTEM TIMLIM=600000 MEMORY=100000000 $END | $SYSTEM TIMLIM=600000 MEMORY=100000000 $END | ||
$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END | $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END | ||
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$DATA | $DATA | ||
BLW-ED Analysis | BLW-ED Analysis | ||
C1 | C1 | ||
| − | + | C 6.0 0.0000000000 0.6097325637 1.7490045499 | |
| − | + | C 6.0 0.0000000000 0.6038280097 0.4085967284 | |
| − | + | C 6.0 0.0000000000 -0.6038307169 -0.4085950903 | |
| − | + | C 6.0 0.0000000000 -0.6097309803 -1.7490029472 | |
| − | + | H 1.0 0.0000000000 1.5343833559 2.3190652626 | |
| − | + | H 1.0 0.0000000000 -0.3149186339 2.3230080652 | |
| − | + | H 1.0 0.0000000000 1.5514513284 -0.1322302753 | |
| − | + | H 1.0 0.0000000000 -1.5514569088 0.1322266423 | |
| + | H 1.0 0.0000000000 -1.5343794820 -2.3190677945 | ||
| + | H 1.0 0.0000000000 0.3149214640 -2.3230051413 | ||
$END | $END | ||
| + | </pre></html> | ||
| − | + | Corresponding files are planar.inp and planar-deconj.inp | |
| − | + | |} | |
| − | + | Localization of px-like pi orbitals to deconjugate keeping planar | |
| − | + | {| class="collapsible collapsed wikitable" | |
| − | + | |- | |
| − | + | !'''BLW part''' | |
| − | + | |- | |
| − | + | | | |
| − | + | px-like pi orbitals on C1=C2 and on C3=C4 | |
| − | + | <html><pre> | |
| − | + | $BLW NBLOCK=3 ITER=50 $END | |
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| − | + | $BLWDAT | |
| − | + | 2 8 0 | |
| − | + | 3 7 13 14 18 22 28 29 | |
| − | + | 2 8 0 | |
| − | $ | + | 33 37 43 44 48 52 58 59 |
| − | + | 26 56 -1 | |
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$END | $END | ||
| − | < | + | </pre></html> |
| − | + | |} | |
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| − | + | ==Evaluation of the hyperconjugaison in the twisted form== | |
| − | < | + | {| class="collapsible collapsed wikitable" |
| − | + | |- | |
| + | !'''Twisted (perpendicular) geometry''' | ||
| + | |- | ||
| + | | | ||
| + | <html><pre> | ||
$contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end | $contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end | ||
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$SYSTEM TIMLIM=600000 MEMORY=100000000 $END | $SYSTEM TIMLIM=600000 MEMORY=100000000 $END | ||
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$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END | $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END | ||
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$DATA | $DATA | ||
BLW-ED Analysis | BLW-ED Analysis | ||
C1 | C1 | ||
| − | + | C 6.0 0.000000 -1.086858 2.236154 | |
| − | + | C 6.0 0.000000 0.000000 1.489418 | |
| − | + | C 6.0 0.000000 0.000000 0.000000 | |
| − | + | C 6.0 -1.086858 0.000000 -0.746736 | |
| − | + | H 1.0 0.967527 0.000000 -0.478451 | |
| − | + | H 1.0 0.000000 0.967527 1.967869 | |
| − | + | H 1.0 -2.072275 0.000000 -0.314213 | |
| − | + | H 1.0 -1.029400 0.000000 -1.820913 | |
| + | H 1.0 0.000000 -2.072275 1.803631 | ||
| + | H 1.0 0.000000 -1.029400 3.310331 | ||
$END | $END | ||
| + | |||
| + | </pre></html> | ||
| + | |} | ||
| + | In the BLW part we localize px-like pi orbitals of atoms C1=C2 and py-like orbitals for C3=C4 to avoid hyperconjugaison. | ||
| + | {| class="collapsible collapsed wikitable" | ||
| + | |- | ||
| + | !'''BLW-Localized part''' | ||
| + | |- | ||
| + | |<html><pre> | ||
| + | $BLW NBLOCK=3 ITER=50 $END | ||
| + | |||
$BLWDAT | $BLWDAT | ||
| − | + | 2 8 0 | |
| − | + | 3 7 13 14 18 22 28 29 | |
| − | 0 | + | 2 8 0 |
| − | + | 34 38 43 45 49 53 58 60 | |
| − | + | 26 56 -1 | |
| − | + | $END | |
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| − | + | </pre></html> | |
| − | </pre> | + | Corresponding files are twisted.inp and twisted-blw.inp |
| − | </html> | + | |} |
| + | |||
| + | :We find | ||
| + | :planar delocalized -155.8824504889 | ||
| + | :planar localized -155.8603462862 (13.9 kcal/mol) | ||
| + | :Perpendicular -155.8695790387 ( 8.1 kcal/mol) | ||
| + | :Perpendicular but localized -155.8537320442 (18.0 kcal/mol) | ||
| + | Hence conjugaison is 13.9 kcal/mol, and the hyper conjugaison in the twisted form is as large as 9.9 kcal/mol | ||
Dernière version du 11 juillet 2012 à 17:33
return to Tutorial n°4 Two geometries are provided the planar and the twisted where a vinyl part C1 C5 has been twisted by 90°. this second moieties has its pi orbitals along the y direction.
Evaluation of the conjugaison
| Planar geometry |
|---|
$contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end $SYSTEM TIMLIM=600000 MEMORY=100000000 $END $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END $DATA BLW-ED Analysis C1 C 6.0 0.0000000000 0.6097325637 1.7490045499 C 6.0 0.0000000000 0.6038280097 0.4085967284 C 6.0 0.0000000000 -0.6038307169 -0.4085950903 C 6.0 0.0000000000 -0.6097309803 -1.7490029472 H 1.0 0.0000000000 1.5343833559 2.3190652626 H 1.0 0.0000000000 -0.3149186339 2.3230080652 H 1.0 0.0000000000 1.5514513284 -0.1322302753 H 1.0 0.0000000000 -1.5514569088 0.1322266423 H 1.0 0.0000000000 -1.5343794820 -2.3190677945 H 1.0 0.0000000000 0.3149214640 -2.3230051413 $END Corresponding files are planar.inp and planar-deconj.inp |
Localization of px-like pi orbitals to deconjugate keeping planar
| BLW part |
|---|
|
px-like pi orbitals on C1=C2 and on C3=C4 $BLW NBLOCK=3 ITER=50 $END $BLWDAT 2 8 0 3 7 13 14 18 22 28 29 2 8 0 33 37 43 44 48 52 58 59 26 56 -1 $END |
Evaluation of the hyperconjugaison in the twisted form
| Twisted (perpendicular) geometry |
|---|
$contrl maxit=200 scftyp=rhf runtyp=ENERGY DFTTYP=B3LYP ICHARG=0 $end $SYSTEM TIMLIM=600000 MEMORY=100000000 $END $BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END $DATA BLW-ED Analysis C1 C 6.0 0.000000 -1.086858 2.236154 C 6.0 0.000000 0.000000 1.489418 C 6.0 0.000000 0.000000 0.000000 C 6.0 -1.086858 0.000000 -0.746736 H 1.0 0.967527 0.000000 -0.478451 H 1.0 0.000000 0.967527 1.967869 H 1.0 -2.072275 0.000000 -0.314213 H 1.0 -1.029400 0.000000 -1.820913 H 1.0 0.000000 -2.072275 1.803631 H 1.0 0.000000 -1.029400 3.310331 $END |
In the BLW part we localize px-like pi orbitals of atoms C1=C2 and py-like orbitals for C3=C4 to avoid hyperconjugaison.
| BLW-Localized part |
|---|
$BLW NBLOCK=3 ITER=50 $END $BLWDAT 2 8 0 3 7 13 14 18 22 28 29 2 8 0 34 38 43 45 49 53 58 60 26 56 -1 $END Corresponding files are twisted.inp and twisted-blw.inp |
- We find
- planar delocalized -155.8824504889
- planar localized -155.8603462862 (13.9 kcal/mol)
- Perpendicular -155.8695790387 ( 8.1 kcal/mol)
- Perpendicular but localized -155.8537320442 (18.0 kcal/mol)
Hence conjugaison is 13.9 kcal/mol, and the hyper conjugaison in the twisted form is as large as 9.9 kcal/mol