[GAMESS] 4-tert-butylcyclohexanone

4-tert-ブチルシクロヘキサノン。カルボニル基への求核付加反応の立体選択性を論じる時に扱われます。いつものようにDFT, B3LYP/6-31G(d)で構造最適化してみました。

-----ここから入力ファイルの中身
! DFT, B3LYP/6-31G(d), optimization
$CONTRL DFTTYP=B3LYP SCFTYP=RHF RUNTYP=OPTIMIZE $END
$SYSTEM TIMLIM=600000 MEMORY=80000000 $END
$STATPT OPTTOL=0.0001 NSTEP=200 PROJCT=.FALSE. $END
$BASIS GBASIS=N31 NGAUSS=6 NDFUNC=1 $END
$GUESS GUESS=HUCKEL $END
$SCF DIRSCF =.TRUE. $END

$DATA

C1
C 6.0 -3.7166284200 2.6885715902 -0.2779868355
C 6.0 -4.9176208181 2.1269944904 0.4481269478
C 6.0 -5.3197436979 0.7882630732 -0.1615745799
H 1.0 -5.7455651141 2.8372144623 0.3530456057
H 1.0 -4.6678087623 2.0240388528 1.5084367733
C 6.0 -2.7352782243 1.6936222066 -0.8515637736
C 6.0 -2.7948468640 0.3931595749 -0.0589285875
H 1.0 -1.7283019473 2.1191542371 -0.7880492389
H 1.0 -2.9819410168 1.5243908992 -1.9047399960
C 6.0 -4.1898286365 -0.2747630779 -0.1331885193
H 1.0 -2.5252678105 0.6034131679 0.9825402974
H 1.0 -2.0354095132 -0.2924763589 -0.4521232817
C 6.0 -4.3971313321 -1.4172484745 0.9299694668
H 1.0 -4.2297661525 -0.7709152475 -1.1154403482
H 1.0 -5.5898057654 0.9613589430 -1.2127690076
H 1.0 -6.2344255273 0.4340866324 0.3212316703
C 6.0 -4.5633546513 -0.8667009067 2.3586849491
C 6.0 -3.1972784298 -2.3900177087 0.9229178125
C 6.0 -5.6534542582 -2.2466890913 0.5783825563
H 1.0 -6.5736476041 -1.6600931878 0.6526273476
H 1.0 -5.7653083735 -3.0995502392 1.2583501647
H 1.0 -5.5899987658 -2.6449491656 -0.4405074395
H 1.0 -3.6922231991 -0.2847672923 2.6746647109
H 1.0 -4.6852360117 -1.6835161579 3.0799874176
H 1.0 -5.4466078938 -0.2265647715 2.4483909362
H 1.0 -2.2811737825 -1.9099758538 1.2826896311
H 1.0 -3.0074531721 -2.7743281559 -0.0855132520
H 1.0 -3.3817863809 -3.2513585657 1.5756470627
O 8.0 -3.5439378630 3.9012157567 -0.3933870203
$END
ここまで-----

最適化構造…tert-ブチル基、でかいです。

↓HOMO (-6.23 eV)。分液漏斗のような軌道が…



↓LUMO (-0.14 eV)。π*軌道の向きと立体周りに注目。