## PO3

 O3 O2 \\ // P1 // O4
The multiplicity is 2.

## Atomic Charges and Dipole Moment

P1 charge= 1.147
O2 charge=-0.383
O3 charge=-0.381
O4 charge=-0.383
with a dipole moment of 0.00984 Debye

## Bond Lengths:

between P1 and O2: distance=1.516 ang___ between P1 and O3: distance=1.516 ang___
between P1 and O4: distance=1.516 ang___ between O2 and O4: distance=2.630 ang___

## Bond Angles:

for O3-P1-O2: angle=119.7 deg___ for O4-P1-O2: angle=120.3 deg___

## Bond Orders (Mulliken):

between P1 and O2: order=1.592___ between P1 and O3: order=1.616___
between P1 and O4: order=1.600___ between O2 and O4: order=0.099___

## 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 P1-O2 with 0.9934 electrons
__has 25.81% P 1 character in a sp1.99 d0.05 hybrid
__has 74.19% O 2 character in a sp2.84 hybrid

2. A bonding orbital for P1-O3 with 0.9953 electrons
__has 25.77% P 1 character in a sp1.86 d0.05 hybrid
__has 74.23% O 3 character in a sp2.41 hybrid

3. A bonding orbital for P1-O4 with 0.9933 electrons
__has 25.84% P 1 character in a sp2.00 d0.05 hybrid
__has 74.16% O 4 character in a sp2.89 hybrid

12. A lone pair orbital for P1 with 0.2335 electrons
__made from a p-pi orbital (100.00% p)

13. A lone pair orbital for O2 with 0.9914 electrons

14. A lone pair orbital for O2 with 0.9631 electrons

15. A lone pair orbital for O2 with 0.9166 electrons
__made from a p-pi orbital ( 99.89% p 0.11% d)

16. A lone pair orbital for O3 with 0.9919 electrons

17. A lone pair orbital for O3 with 0.9544 electrons
__made from a p-pi orbital ( 99.91% p 0.09% d)

18. A lone pair orbital for O3 with 0.9078 electrons
__made from a p-pi orbital ( 99.90% p 0.10% d)

19. A lone pair orbital for O4 with 0.9913 electrons

20. A lone pair orbital for O4 with 0.9636 electrons

21. A lone pair orbital for O4 with 0.9166 electrons
__made from a p-pi orbital ( 99.89% p 0.11% d)

-With core pairs on: P 1 P 1 P 1 P 1 P 1 O 2 O 3 O 4 -

#### Up Electrons

1. A bonding orbital for P1-O2 with 0.9453 electrons
__has 31.02% P 1 character in a sp2.68 d0.09 hybrid
__has 68.98% O 2 character in a s0.97 p3 hybrid

2. A bonding orbital for P1-O3 with 0.8774 electrons
__has 48.02% P 1 character in a sp1.14 hybrid
__has 51.98% O 3 character in a s0.17 p3 hybrid

3. A bonding orbital for P1-O4 with 0.9521 electrons
__has 30.47% P 1 character in a sp2.62 d0.08 hybrid
__has 69.53% O 4 character in a s0.98 p3 hybrid

4. A antibonding orbital for O2-O4 with 0.9508 electrons
__has 50.78% O 2 character in a s0.16 p3 hybrid
__has 49.22% O 4 character in a s0.13 p3 hybrid

13. A lone pair orbital for P1 with 0.2868 electrons
__made from a p-pi orbital ( 99.99% p)

14. A lone pair orbital for O2 with 0.9889 electrons

15. A lone pair orbital for O2 with 0.8979 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

16. A lone pair orbital for O3 with 0.9600 electrons
__made from a s0.83 p3 hybrid

17. A lone pair orbital for O3 with 0.9532 electrons

18. A lone pair orbital for O3 with 0.8853 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

19. A lone pair orbital for O4 with 0.9898 electrons

20. A lone pair orbital for O4 with 0.8981 electrons
__made from a p-pi orbital ( 99.88% p 0.12% d)

103. A bonding orbital for O2-O4 with 0.2491 electrons
__has 49.22% O 2 character in a s0.16 p3 hybrid
__has 50.78% O 4 character in a s0.13 p3 hybrid

-With core pairs on: P 1 P 1 P 1 P 1 P 1 O 2 O 3 O 4 -

#### 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 bonding donor orbital, 1, for P1-O2 with the bonding acceptor orbital, 103, for O2-O4 is 105. kJ/mol.

The interaction of bonding donor orbital, 2, for P1-O3 with the bonding acceptor orbital, 103, for O2-O4 is 78.9 kJ/mol.

The interaction of bonding donor orbital, 3, for P1-O4 with the bonding acceptor orbital, 103, for O2-O4 is 92.6 kJ/mol.

The interaction of antibonding donor orbital, 4, for O2-O4 with the antibonding acceptor orbital, 100, for P1-O2 is 37.4 kJ/mol.

The interaction of antibonding donor orbital, 4, for O2-O4 with the antibonding acceptor orbital, 102, for P1-O4 is 27.5 kJ/mol.

The interaction of the second lone pair donor orbital, 15, for O2 with the lone pair acceptor orbital, 13, for P1 is 214. kJ/mol.

The interaction of lone pair donor orbital, 16, for O3 with the antibonding acceptor orbital, 102, for P1-O4 is 39.7 kJ/mol.

The interaction of the second lone pair donor orbital, 17, for O3 with the antibonding acceptor orbital, 100, for P1-O2 is 26.2 kJ/mol.

The interaction of the second lone pair donor orbital, 17, for O3 with the antibonding acceptor orbital, 101, for P1-O3 is 20.1 kJ/mol.

The interaction of the third lone pair donor orbital, 18, for O3 with the lone pair acceptor orbital, 13, for P1 is 250. kJ/mol.

The interaction of the second lone pair donor orbital, 20, for O4 with the lone pair acceptor orbital, 13, for P1 is 213. 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.

24 ----- 1.985
23 ----- 1.949

22 ----- -3.127

21 ----- -3.410

20 -^--- -9.294

19 -^-v- -9.803 18 -^-v- -9.805

17 -^-v- -10.59
16 -^-v- -10.60

15 -^-v- -12.27

14 -^-v- -12.47 13 -^-v- -12.48

12 -^-v- -14.60

11 -^-v- -26.20 10 -^-v- -26.20

9 -^-v- -28.16

8 -^-v- -127.4 7 -^-v- -127.4

6 -^-v- -127.7

5 -^-v- -175.1

4 -^-v- -509.1 3 -^-v- -509.1 2 -^-v- -509.1

1 -^-v- -2072.

## 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 = -567.1400812239 Hartrees