Новосибирский институт органической химии им. Н.Н. Ворожцова СО РАН

Лаборатория изучения механизмов органических реакций

All the data in zip-archive

C6H6 + nBr2 ➙ C6H5Br + HBr + (n-1)Br2 (n = 1, 2, 3)

See Henry Rzepa blog.

Geometry optimization by DFT/PBE/L1 (PRIRODA program, basis like cc-pVDZ)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-14.29 -14.29 -8.68 -8.68 16.81 16.81 -20.51 -20.51 -15.92 -15.92 -0.55 -0.55 -9.99 -9.99 -3.68 -3.68 41.43 41.43

Summary energy of noninteracting reagents is taken to be zero energy.

With thermochemistry corrections


-2.69 -2.69 6.84 6.84 34.38 34.38 -1.29 -1.29 9.69 9.69 26.50 26.50 -4.83 -4.83 2.43 2.43 48.84 48.84

C6H6 + Br2 PES

cf. J. Kong, B. Galabov, G. Koleva, J.-J. Zou, H. F. Schaefer III, and P.v.R. Schleyer, Angew. Chem. Int. Ed. 2011, 50, 6809-6813


On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-9.99 -9.99 -3.65 -3.65 7.21 7.21 8.18 8.18 8.63 8.63 13.01 13.01 30.04 30.04 32.52 32.52 37.18 37.18 38.34 38.34 40.23 40.23 41.04 41.04 41.43 41.43 41.50 41.50 42.69 42.69

C6H6 + 2Br2 PES

Geometry optimization by DFT/PBE/L1 (PRIRODA program, basis like cc-pVDZ)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-15.81 -15.81 -14.35 -14.35 -14.26 -14.26 -8.68 -8.68 0.59 0.59 1.11 1.11 1.20 1.20 1.31 1.31 1.54 1.54 1.71 1.71 2.53 2.53 3.01 3.01 3.92 3.92 5.13 5.13 5.47 5.47 5.82 5.82 6.46 6.46 9.22 9.22 9.96 9.96 11.57 11.57 11.61 11.61 12.27 12.27 12.34 12.34 13.30 13.30 13.89 13.89 14.55 14.55 16.81 16.81 17.02 17.02 17.41 17.41 18.93 18.93 18.95 18.95 19.58 19.58 21.43 21.43

Summary energy of noninteracting reagents is taken to be zero energy.

C6H6 + 3Br2 PES

Geometry optimization by DFT/PBE/L1 (PRIRODA program, basis like of cc-pVDZ)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

-20.51 -20.51 -20.13 -20.13 -18.92 -18.92 -18.12 -18.12 -15.92 -15.92 -15.11 -15.11 -11.97 -11.97 -10.68 -10.68 -8.25 -8.25 -6.33 -6.33 -5.62 -5.62 -4.91 -4.91 -4.82 -4.82 -4.63 -4.63 -4.57 -4.57 -4.32 -4.32 -4.03 -4.03 -3.14 -3.14 -3.01 -3.01 -2.20 -2.20 -1.92 -1.92 -0.93 -0.93 -0.55 -0.55 0.86 0.86 0.95 0.95 1.35 1.35 1.59 1.59 2.11 2.11 4.77 4.77 7.87 7.87 12.20 12.20 -3.00 -3.00
Summary energy of noninteracting reagents is taken to be zero energy.

Additional C6H6 + 3Br2 PES

Starting structures for transition states (PhHBr+ + Br5-) was found by Coalescence Kick (CK) method .
CK method: Sergeeva A.P., Averkiev B.B., Zhai H.-J., Boldyrev A.I., and Wang L.-S. J. Chem. Phys. 134, 224304 (2011)

-22.47 -22.47 -20.40 -20.40 -20.13 -20.13 -18.85 -18.85 -15.85 -15.85 -6.59 -6.59 -6.33 -6.33 -4.68 -4.68 -4.68 -4.68 -4.64 -4.64 -4.63 -4.63 -4.57 -4.57 -3.56 -3.56 -3.43 -3.43 -3.11 -3.11 -2.94 -2.94 -2.79 -2.79 -2.70 -2.70 -1.83 -1.83 -1.77 -1.77 -0.50 -0.50 1.86 1.86 3.23 3.23 3.28 3.28 3.96 3.96 4.11 4.11 4.36 4.36 4.38 4.38 6.35 6.35 6.52 6.52 9.10 9.10


Summary energy of noninteracting reagents is taken to be zero energy.

Relaxation of high-energy complex PhBr_8a (PhBr+HBr3+Br2)

-22.47 -22.47 -20.40 -20.40 -18.85 -18.85 -17.11 -17.11 -10.68 -10.68 -9.04 -9.04 -8.49 -8.49 -8.25 -8.25 -8.24 -8.24 -7.70 -7.70 -7.28 -7.28 -7.02 -7.02 -6.95 -6.95 -4.47 -4.47 -4.03 -4.03 -3.89 -3.89 -3.35 -3.35 -3.14 -3.14 -2.35 -2.35 0.74 0.74 1.07 1.07

Summary energy of noninteracting reagents is taken to be zero energy.

Conformational analysis of 3,4,5,6-tetrabromocyclohexene

Methods of conformational anlysis: MM (Marvin) — MP2 (PRIRODA).
Energy (without ZPE) by riMP2/L1 (cc-pVDZ, PRIRODA program)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

0.00 0.00 3.82 3.82 3.92 3.92 3.99 3.99 4.14 4.14 4.29 4.29 4.46 4.46 4.81 4.81 5.05 5.05 8.27 8.27 9.34 9.34 11.07 11.07 13.06 13.06 13.20 13.20 13.61 13.61 15.88 15.88 16.41 16.41 16.41 16.41 16.49 16.49 18.63 18.63 20.32 20.32 20.44 20.44
Methods of conformational anlysis: MM (Marvin) — DFT (PRIRODA).
Energy (without ZPE) by DFT/PBE/L1 (cc-pVDZ, PRIRODA program)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

0.00 0.00 2.67 2.67 3.32 3.32 3.51 3.51 3.54 3.54 3.64 3.64 3.93 3.93 4.48 4.48 4.75 4.75 7.09 7.09 9.41 9.41 10.63 10.63 10.70 10.70 12.09 12.09 12.43 12.43 12.93 12.93 14.47 14.47 14.87 14.87 14.87 14.87 16.94 16.94 18.00 18.00 20.62 20.62

Conformational analysis of 3,4,6-tribromocyclohexene


Energy (without ZPE) by riMP2/L1 (cc-pVDZ, PRIRODA program)

On figure(s) below click on the level title to download xyz file ==>
Click on energy level to view 3D structure in browser (run JSmol) ==>

0.00 0.00 1.18 1.18 1.34 1.34 2.08 2.08 2.55 2.55 2.95 2.95 3.90 3.90 7.68 7.68