## ClOO, chlorine peroxide (*see note)

 O3 \ O1 - CL2
The multiplicity is 2.

## Atomic Charges and Dipole Moment

O1 charge= 0.083
CL2 charge=-0.092
O3 charge= 0.009
with a dipole moment of 0.81283 Debye

## Bond Lengths:

between O1 and CL2: distance=2.029 ang___ between O1 and O3: distance=1.238 ang___
between CL2 and O3: distance=2.815 ang___

## Bond Angles:

for O3-O1-CL2: angle=116.9 deg___

## Bond Orders (Mulliken):

between O1 and CL2: order=0.731___ between O1 and O3: order=1.208___
between CL2 and O3: order=0.187___

## Best Lewis Structure

The Lewis structure that is closest to your structure is determined. The hybridization of the atoms in this idealized Lewis structure is given in the table below. The Lewis structure is built for the up and down electrons, separately. Note that the up and down structures can be very different.

### Hybridization in the Best Lewis Structure

#### Down Electrons

1. A bonding orbital for O1-Cl2 with 0.9971 electrons
__has 53.17% O 1 character in a s0.10 p3 hybrid
__has 46.83% Cl 2 character in a s0.09 p3 hybrid

2. A bonding orbital for O1-O3 with 0.9989 electrons
__has 51.17% O 1 character in a s0.73 p3 hybrid
__has 48.83% O 3 character in a s0.64 p3 hybrid

10. A lone pair orbital for O1 with 0.9995 electrons

11. A lone pair orbital for O1 with 0.9975 electrons
__made from a p-pi orbital ( 99.97% p)

12. A lone pair orbital for Cl2 with 0.9999 electrons

13. A lone pair orbital for Cl2 with 0.9999 electrons
__made from a p-pi orbital (100.00% p)

14. A lone pair orbital for Cl2 with 0.9978 electrons
__made from a s0.48 p3 hybrid

15. A lone pair orbital for O3 with 0.9993 electrons

16. A lone pair orbital for O3 with 0.9985 electrons
__made from a p-pi orbital ( 99.97% p)

17. A lone pair orbital for O3 with 0.9157 electrons
__made from a s0.06 p3 hybrid

-With core pairs on: O 1 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 O 3 -

#### Up Electrons

1. A bonding orbital for O1-Cl2 with 0.9961 electrons
__has 58.76% O 1 character in a s0.15 p3 hybrid
__has 41.24% Cl 2 character in a s0.08 p3 hybrid

2. A bonding orbital for O1-O3 with 0.9986 electrons
__has 54.32% O 1 character in a s0.86 p3 hybrid
__has 45.68% O 3 character in a s0.76 p3 hybrid

3. A bonding orbital for O1-O3 with 0.9997 electrons
__has 82.46% O 1 character in a p-pi orbital ( 99.86% p 0.14% d)
__has 17.54% O 3 character in a p-pi orbital ( 99.43% p 0.57% d)

11. A lone pair orbital for O1 with 0.9992 electrons

12. A lone pair orbital for Cl2 with 0.9999 electrons

13. A lone pair orbital for Cl2 with 0.9983 electrons
__made from a s0.60 p3 hybrid

14. A lone pair orbital for Cl2 with 0.9980 electrons
__made from a p-pi orbital (100.00% p)

15. A lone pair orbital for O3 with 0.9991 electrons

16. A lone pair orbital for O3 with 0.9033 electrons
__made from a s0.07 p3 hybrid

-With core pairs on: O 1 Cl 2 Cl 2 Cl 2 Cl 2 Cl 2 O 3 -

#### Donor Acceptor Interactions in the Best Lewis Structure

The localized orbitals in your best Lewis structure can interact strongly. A filled bonding or lone pair orbital can act as a donor and an empty or filled bonding, antibonding, or lone pair orbital can act as an acceptor. These interactions can strengthen and weaken bonds. For example, a lone pair donor->antibonding acceptor orbital interaction will weaken the bond associated with the antibonding orbital. Conversly, an interaction with a bonding pair as the acceptor will strengthen the bond. Strong electron delocalization in your best Lewis structure will also show up as donor-acceptor interactions.
Interactions greater than 20 kJ/mol for bonding and lone pair orbitals are listed below.

The interaction of the second lone pair donor orbital, 16, for O3 with the antibonding acceptor orbital, 77, for O1-Cl2 is 161. kJ/mol.

## Molecular Orbital Energies

The orbital energies are given in eV, where 1 eV=96.49 kJ/mol. Orbitals with very low energy are core 1s orbitals. More antibonding orbitals than you might expect are sometimes listed, because d orbitals are always included for heavy atoms and p orbitals are included for H atoms. Up spins are shown with a ^ and down spins are shown as v. Only the spin up electron orbital energies are given.

21 ----- 6.803
20 ----- 6.376

19 ----- 1.508

18 ----- -6.018

17 -^--- -7.384

16 -^-v- -8.031

15 -^-v- -8.441

14 -^-v- -8.700

13 -^-v- -14.08

12 -^-v- -14.21

11 -^-v- -14.65

10 -^-v- -19.60

9 -^-v- -22.00

8 -^-v- -33.28

7 -^-v- -190.7
6 -^-v- -190.7

5 -^-v- -191.2

4 -^-v- -249.2

3 -^-v- -511.1

2 -^-v- -512.6

1 -^-v- -2730.

## Total Electronic Energy

The total electronic energy is a very large number, so by convention the units are given in atomic units, that is Hartrees (H). One Hartree is 2625.5 kJ/mol. The energy reference is for totally dissociated atoms. In other words, the reference state is a gas consisting of nuclei and electrons all at infinite distance from each other. The electronic energy includes all electric interactions and the kinetic energy of the electrons. This energy does not include translation, rotation, or vibration of the the molecule.

Total electronic energy = -610.5947094400 Hartrees

*Note: ClO2 is higher in energy in these calculations, however, ClO2 appears to be the more stable, observed form.