## H2C=COHCH3+•, propenol radical cation, (see note)

 H5 H7 | / H6 - C4 H3 \ / C1 - O2 // H10 - C8 \ H9
The ion charge is 1. The multiplicity is 2.

## Atomic Charges and Dipole Moment

C1 charge= 0.564
O2 charge=-0.401
H3 charge= 0.483
C4 charge=-0.677
H5 charge= 0.252
H6 charge= 0.257
H7 charge= 0.253
C8 charge=-0.165
H9 charge= 0.228
H10 charge= 0.204
with a dipole moment of 0.95623 Debye

## Bond Lengths:

between C1 and O2: distance=1.322 ang___ between C1 and C4: distance=1.482 ang___
between C1 and C8: distance=1.425 ang___ between O2 and H3: distance=0.989 ang___
between O2 and C8: distance=2.304 ang___ between C4 and H5: distance=1.110 ang___
between C4 and H6: distance=1.100 ang___ between C4 and H7: distance=1.110 ang___
between C4 and C8: distance=2.576 ang___ between C8 and H9: distance=1.097 ang___
between C8 and H10: distance=1.095 ang___

## Bond Angles:

for H3-O2-C1: angle=113.4 deg___ for C4-C1-O2: angle=121.2 deg___
for H5-C4-C1: angle=110.2 deg___ for H6-C4-C1: angle=112.1 deg___
for H7-C4-C1: angle=110.2 deg___ for C8-C1-O2: angle=113.9 deg___
for H9-C8-C1: angle=119.7 deg___ for H10-C8-C1: angle=120.3 deg___

## Bond Orders (Mulliken):

between C1 and O2: order=1.267___ between C1 and C4: order=0.814___
between C1 and C8: order=1.186___ between O2 and H3: order=0.796___
between O2 and C8: order=-0.085___ between C4 and H5: order=0.930___
between C4 and H6: order=0.982___ between C4 and H7: order=0.931___
between C4 and C8: order=-0.079___ between C8 and H9: order=0.950___
between C8 and H10: order=0.933___

## 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 C1-O2 with 0.9982 electrons
__has 32.76% C 1 character in a sp2.63 hybrid
__has 67.24% O 2 character in a sp1.88 hybrid

2. A bonding orbital for C1-C4 with 0.9964 electrons
__has 52.57% C 1 character in a sp1.65 hybrid
__has 47.43% C 4 character in a sp2.77 hybrid

3. A bonding orbital for C1-C8 with 0.9950 electrons
__has 51.70% C 1 character in a sp1.84 hybrid
__has 48.30% C 8 character in a sp1.88 hybrid

4. A bonding orbital for C1-C8 with 0.9944 electrons
__has 28.82% C 1 character in a p3 hybrid
__has 71.18% C 8 character in a p3 hybrid

5. A bonding orbital for O2-H3 with 0.9935 electrons
__has 77.36% O 2 character in a s0.88 p3 hybrid
__has 22.64% H 3 character in a s orbital

6. A bonding orbital for C4-H5 with 0.9856 electrons
__has 62.61% C 4 character in a s0.94 p3 hybrid
__has 37.39% H 5 character in a s orbital

7. A bonding orbital for C4-H6 with 0.9929 electrons
__has 62.69% C 4 character in a sp2.89 hybrid
__has 37.31% H 6 character in a s orbital

8. A bonding orbital for C4-H7 with 0.9857 electrons
__has 62.60% C 4 character in a s0.94 p3 hybrid
__has 37.40% H 7 character in a s orbital

9. A bonding orbital for C8-H9 with 0.9943 electrons
__has 63.45% C 8 character in a sp2.02 hybrid
__has 36.55% H 9 character in a s orbital

10. A bonding orbital for C8-H10 with 0.9937 electrons
__has 62.77% C 8 character in a sp2.07 hybrid
__has 37.23% H10 character in a s orbital

15. A lone pair orbital for O2 with 0.9899 electrons

16. A lone pair orbital for O2 with 0.9307 electrons
__made from a p-pi orbital ( 99.92% p 0.08% d)

-With core pairs on: C 1 O 2 C 4 C 8 -

#### Up Electrons

1. A bonding orbital for C1-O2 with 0.9982 electrons
__has 33.33% C 1 character in a sp2.63 hybrid
__has 66.67% O 2 character in a sp1.84 hybrid

2. A bonding orbital for C1-O2 with 0.9914 electrons
__has 18.29% C 1 character in a p-pi orbital ( 99.28% p 0.72% d)
__has 81.71% O 2 character in a p-pi orbital ( 99.89% p 0.11% d)

3. A bonding orbital for C1-C4 with 0.9964 electrons
__has 52.02% C 1 character in a sp1.70 hybrid
__has 47.98% C 4 character in a sp2.75 hybrid

4. A bonding orbital for C1-C8 with 0.9948 electrons
__has 54.20% C 1 character in a sp1.80 hybrid
__has 45.80% C 8 character in a sp1.91 hybrid

5. A bonding orbital for O2-H3 with 0.9939 electrons
__has 76.58% O 2 character in a s0.88 p3 hybrid
__has 23.42% H 3 character in a s orbital

6. A bonding orbital for C4-H5 with 0.9807 electrons
__has 63.34% C 4 character in a s0.94 p3 hybrid
__has 36.66% H 5 character in a s orbital

7. A bonding orbital for C4-H6 with 0.9931 electrons
__has 62.72% C 4 character in a sp2.89 hybrid
__has 37.28% H 6 character in a s orbital

8. A bonding orbital for C4-H7 with 0.9808 electrons
__has 63.33% C 4 character in a s0.94 p3 hybrid
__has 36.67% H 7 character in a s orbital

9. A bonding orbital for C8-H9 with 0.9952 electrons
__has 59.55% C 8 character in a sp2.02 hybrid
__has 40.45% H 9 character in a s orbital

10. A bonding orbital for C8-H10 with 0.9946 electrons
__has 58.79% C 8 character in a sp2.06 hybrid
__has 41.21% H10 character in a s orbital

15. A lone pair orbital for O2 with 0.9895 electrons

-With core pairs on: C 1 O 2 C 4 C 8 -

#### 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, 6, for C4-H5 with the second antibonding acceptor orbital, 124, for C1-O2 is 23.5 kJ/mol.

The interaction of bonding donor orbital, 8, for C4-H7 with the second antibonding acceptor orbital, 124, for C1-O2 is 23.3 kJ/mol.

The interaction of the second antibonding donor orbital, 124, for C1-O2 with the lone pair acceptor orbital, 16, for C8 is 26.9 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.

20 ----- -2.889

19 ----- -3.116

18 ----- -5.254

17 ----- -8.091

16 -^--- -12.96

15 -^-v- -15.28

14 -^-v- -15.49
13 -^-v- -15.52

12 -^-v- -16.68

11 -^-v- -17.74

10 -^-v- -18.16

9 -^-v- -18.90

8 -^-v- -21.88

7 -^-v- -23.90

6 -^-v- -26.20

5 -^-v- -34.11

4 -^-v- -272.4

3 -^-v- -274.0

2 -^-v- -276.0

1 -^-v- -515.0

## 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 = -192.8868268876 Hartrees

*This ion results from the McLafferty rearrangment of 2-pentanone radical cation (propylmethyl ketone radical cation). The ion, of course, can also be created directly from the enol tautomer of propanone.