## PF4- ion

 F3 F2 \ / F5 - P1 / F4
The ion charge is -1.

## Atomic Charges and Dipole Moment

P1 charge= 0.250
F2 charge=-0.442
F3 charge=-0.184
F4 charge=-0.180
F5 charge=-0.442
with a dipole moment of 0.09364 Debye

## Bond Lengths:

between P1 and F2: distance=1.827 ang___ between P1 and F3: distance=1.683 ang___
between P1 and F4: distance=1.676 ang___ between P1 and F5: distance=1.825 ang___

## Bond Angles:

for F3-P1-F2: angle=88.11 deg___ for F4-P1-F2: angle=86.95 deg___
for F5-P1-F2: angle=171.9 deg___

## Bond Orders (Mulliken):

between P1 and F2: order=0.412___ between P1 and F3: order=0.699___
between P1 and F4: order=0.709___ between P1 and F5: order=0.412___

## 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.

### Hybridization in the Best Lewis Structure

1. A bonding orbital for P1-F2 with 1.9546 electrons
__has 9.66% P 1 character in a s0.49 p3 d1.70 hybrid
__has 90.34% F 2 character in a s0.72 p3 hybrid

2. A bonding orbital for P1-F3 with 1.9718 electrons
__has 15.02% P 1 character in a s0.36 p3 d0.43 hybrid
__has 84.98% F 3 character in a s0.90 p3 hybrid

3. A bonding orbital for P1-F4 with 1.9698 electrons
__has 14.96% P 1 character in a s0.38 p3 d0.47 hybrid
__has 85.04% F 4 character in a s0.91 p3 hybrid

4. A bonding orbital for P1-F5 with 1.9545 electrons
__has 9.68% P 1 character in a s0.49 p3 d1.70 hybrid
__has 90.32% F 5 character in a s0.72 p3 hybrid

14. A lone pair orbital for P1 with 1.9915 electrons

15. A lone pair orbital for F2 with 1.9970 electrons

16. A lone pair orbital for F2 with 1.9898 electrons
__made from a s0.11 p3 hybrid

17. A lone pair orbital for F2 with 1.9814 electrons

18. A lone pair orbital for F3 with 1.9956 electrons

19. A lone pair orbital for F3 with 1.9826 electrons
__made from a p-pi orbital ( 99.98% p)

20. A lone pair orbital for F3 with 1.9744 electrons

21. A lone pair orbital for F4 with 1.9954 electrons

22. A lone pair orbital for F4 with 1.9829 electrons
__made from a p-pi orbital ( 99.98% p)

23. A lone pair orbital for F4 with 1.9733 electrons

24. A lone pair orbital for F5 with 1.9970 electrons

25. A lone pair orbital for F5 with 1.9897 electrons
__made from a s0.11 p3 hybrid

26. A lone pair orbital for F5 with 1.9814 electrons
__made from a p-pi orbital ( 99.99% p)

-With core pairs on: P 1 P 1 P 1 P 1 P 1 F 2 F 3 F 4 F 5 -

#### 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-F2 with the antibonding acceptor orbital, 125, for P1-F3 is 52.1 kJ/mol.

The interaction of bonding donor orbital, 1, for P1-F2 with the antibonding acceptor orbital, 126, for P1-F4 is 56.4 kJ/mol.

The interaction of bonding donor orbital, 1, for P1-F2 with the antibonding acceptor orbital, 127, for P1-F5 is 148. kJ/mol.

The interaction of bonding donor orbital, 2, for P1-F3 with the antibonding acceptor orbital, 124, for P1-F2 is 68.0 kJ/mol.

The interaction of bonding donor orbital, 2, for P1-F3 with the antibonding acceptor orbital, 127, for P1-F5 is 68.3 kJ/mol.

The interaction of bonding donor orbital, 3, for P1-F4 with the antibonding acceptor orbital, 124, for P1-F2 is 74.3 kJ/mol.

The interaction of bonding donor orbital, 3, for P1-F4 with the antibonding acceptor orbital, 127, for P1-F5 is 74.3 kJ/mol.

The interaction of bonding donor orbital, 4, for P1-F5 with the antibonding acceptor orbital, 124, for P1-F2 is 148. kJ/mol.

The interaction of bonding donor orbital, 4, for P1-F5 with the antibonding acceptor orbital, 125, for P1-F3 is 52.5 kJ/mol.

The interaction of bonding donor orbital, 4, for P1-F5 with the antibonding acceptor orbital, 126, for P1-F4 is 56.5 kJ/mol.

The interaction of lone pair donor orbital, 15, for F2 with the antibonding acceptor orbital, 127, for P1-F5 is 25.2 kJ/mol.

The interaction of the third lone pair donor orbital, 20, for F3 with the antibonding acceptor orbital, 126, for P1-F4 is 35.6 kJ/mol.

The interaction of the third lone pair donor orbital, 23, for F4 with the antibonding acceptor orbital, 125, for P1-F3 is 37.7 kJ/mol.

The interaction of lone pair donor orbital, 24, for F5 with the antibonding acceptor orbital, 124, for P1-F2 is 25.4 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.

30 ----- 9.976

29 ----- 6.263

28 ----- 5.522

27 ----- 3.953

26 -^-v- -1.019

25 -^-v- -2.968

24 -^-v- -3.090

23 -^-v- -3.344

22 -^-v- -3.463

21 -^-v- -4.506

20 -^-v- -4.658

19 -^-v- -5.036

18 -^-v- -5.247

17 -^-v- -6.333

16 -^-v- -6.798

15 -^-v- -7.473

14 -^-v- -10.54

13 -^-v- -21.92

12 -^-v- -22.06

11 -^-v- -23.86

10 -^-v- -24.69

9 -^-v- -120.6

8 -^-v- -120.8
7 -^-v- -120.9

6 -^-v- -168.3

5 -^-v- -648.7 4 -^-v- -648.7

3 -^-v- -650.4 2 -^-v- -650.4

1 -^-v- -2066.

## 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 = -741.1086875295 Hartrees