## CH3COH=CHCH2CH2+•, pentenol radical cation all trans-conformer, (see note)

 H7 \ C5 - H6 / H9 - C4 | \ H10 - C3 H8 / \ O1 - C2 H14 H11 / \ | H16 C12 - H13 / H15
The ion charge is 1. The multiplicity is 2.

## Atomic Charges and Dipole Moment

O1 charge=-0.411
C2 charge= 0.471
C3 charge=-0.331
C4 charge= 0.124
C5 charge=-0.324
H6 charge= 0.200
H7 charge= 0.200
H8 charge= 0.066
H9 charge= 0.082
H10 charge= 0.198
H11 charge= 0.165
C12 charge=-0.639
H13 charge= 0.254
H14 charge= 0.248
H15 charge= 0.220
H16 charge= 0.473
with a dipole moment of 8.51863 Debye

## Bond Lengths:

between O1 and C2: distance=1.319 ang___ between O1 and H16: distance=0.986 ang___
between C2 and C3: distance=1.460 ang___ between C2 and C12: distance=1.482 ang___
between C3 and C4: distance=1.673 ang___ between C3 and H10: distance=1.101 ang___
between C3 and H11: distance=1.100 ang___ between C4 and C5: distance=1.462 ang___
between C4 and H8: distance=1.103 ang___ between C4 and H9: distance=1.104 ang___
between C5 and H6: distance=1.096 ang___ between C5 and H7: distance=1.096 ang___
between C12 and H13: distance=1.111 ang___ between C12 and H14: distance=1.106 ang___
between C12 and H15: distance=1.103 ang___

## Bond Angles:

for C3-C2-O1: angle=115.3 deg___ for C4-C3-C2: angle=109.1 deg___
for C5-C4-C3: angle=108.9 deg___ for H6-C5-C4: angle=120.9 deg___
for H7-C5-C4: angle=120.7 deg___ for H8-C4-C3: angle=106.8 deg___
for H9-C4-C3: angle=105.3 deg___ for H10-C3-C2: angle=111.2 deg___
for H11-C3-C2: angle=111.1 deg___ for C12-C2-O1: angle=121.0 deg___
for H13-C12-C2: angle=108.5 deg___ for H14-C12-C2: angle=110.7 deg___
for H15-C12-C2: angle=113.7 deg___ for H16-O1-C2: angle=112.9 deg___

## Bond Orders (Mulliken):

between O1 and C2: order=1.427___ between O1 and H16: order=0.838___
between C2 and C3: order=1.005___ between C2 and C12: order=1.050___
between C3 and C4: order=0.790___ between C3 and H10: order=0.951___
between C3 and H11: order=0.962___ between C4 and C5: order=0.978___
between C4 and H8: order=0.971___ between C4 and H9: order=0.971___
between C5 and H6: order=0.956___ between C5 and H7: order=0.957___
between C12 and H13: order=0.899___ between C12 and H14: order=0.933___
between C12 and H15: order=0.944___

## 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-C2 with 0.9976 electrons
__has 67.94% O 1 character in a sp1.81 hybrid
__has 32.06% C 2 character in a sp2.67 hybrid

2. A bonding orbital for O1-C2 with 0.9971 electrons
__has 86.71% O 1 character in a p3 hybrid
__has 13.29% C 2 character in a p3 hybrid

3. A bonding orbital for O1-H16 with 0.9935 electrons
__has 76.67% O 1 character in a s0.87 p3 hybrid
__has 23.33% H16 character in a s orbital

4. A bonding orbital for C2-C3 with 0.9929 electrons
__has 51.87% C 2 character in a sp1.69 hybrid
__has 48.13% C 3 character in a sp2.75 hybrid

5. A bonding orbital for C2-C12 with 0.9955 electrons
__has 51.01% C 2 character in a sp1.78 hybrid
__has 48.99% C12 character in a sp2.63 hybrid

6. A bonding orbital for C3-C4 with 0.9501 electrons
__has 59.40% C 3 character in a s0.95 p3 hybrid
__has 40.60% C 4 character in a s0.76 p3 hybrid

7. A bonding orbital for C3-H10 with 0.9866 electrons
__has 63.01% C 3 character in a s0.99 p3 hybrid
__has 36.99% H10 character in a s orbital

8. A bonding orbital for C3-H11 with 0.9870 electrons
__has 62.02% C 3 character in a s0.97 p3 hybrid
__has 37.98% H11 character in a s orbital

9. A bonding orbital for C4-C5 with 0.9955 electrons
__has 52.20% C 4 character in a sp2.17 hybrid
__has 47.80% C 5 character in a sp1.77 hybrid

10. A bonding orbital for C4-H8 with 0.9941 electrons
__has 59.38% C 4 character in a s0.95 p3 hybrid
__has 40.62% H 8 character in a s orbital

11. A bonding orbital for C4-H9 with 0.9935 electrons
__has 59.92% C 4 character in a s0.96 p3 hybrid
__has 40.08% H 9 character in a s orbital

12. A bonding orbital for C5-H6 with 0.9953 electrons
__has 61.49% C 5 character in a sp2.13 hybrid
__has 38.51% H 6 character in a s orbital

13. A bonding orbital for C5-H7 with 0.9952 electrons
__has 61.55% C 5 character in a sp2.13 hybrid
__has 38.45% H 7 character in a s orbital

14. A bonding orbital for C12-H13 with 0.9766 electrons
__has 63.38% C12 character in a s0.90 p3 hybrid
__has 36.62% H13 character in a s orbital

15. A bonding orbital for C12-H14 with 0.9847 electrons
__has 62.97% C12 character in a s0.96 p3 hybrid
__has 37.03% H14 character in a s orbital

16. A bonding orbital for C12-H15 with 0.9937 electrons
__has 61.76% C12 character in a sp2.96 hybrid
__has 38.24% H15 character in a s orbital

23. A lone pair orbital for O1 with 0.9895 electrons

24. A lone pair orbital for C5 with 0.9437 electrons

166. A antibonding orbital for O1-C2 with 0.1003 electrons
__has 13.29% O 1 character in a p3 hybrid
__has 86.71% C 2 character in a p3 hybrid

-With core pairs on: O 1 C 2 C 3 C 4 C 5 C12 -

#### Up Electrons

1. A bonding orbital for O1-C2 with 0.9979 electrons
__has 67.86% O 1 character in a sp1.79 hybrid
__has 32.14% C 2 character in a sp2.64 hybrid

2. A bonding orbital for O1-C2 with 0.9971 electrons
__has 86.46% O 1 character in a p-pi orbital ( 99.90% p 0.10% d)
__has 13.54% C 2 character in a p3 hybrid

3. A bonding orbital for O1-H16 with 0.9934 electrons
__has 76.64% O 1 character in a s0.87 p3 hybrid
__has 23.36% H16 character in a s orbital

4. A bonding orbital for C2-C3 with 0.9927 electrons
__has 51.53% C 2 character in a sp1.71 hybrid
__has 48.47% C 3 character in a sp2.58 hybrid

5. A bonding orbital for C2-C12 with 0.9954 electrons
__has 50.91% C 2 character in a sp1.78 hybrid
__has 49.09% C12 character in a sp2.63 hybrid

6. A bonding orbital for C3-C4 with 0.9584 electrons
__has 52.39% C 3 character in a s0.88 p3 hybrid
__has 47.61% C 4 character in a s0.77 p3 hybrid

7. A bonding orbital for C3-H10 with 0.9873 electrons
__has 62.44% C 3 character in a s0.99 p3 hybrid
__has 37.56% H10 character in a s orbital

8. A bonding orbital for C3-H11 with 0.9876 electrons
__has 61.45% C 3 character in a s0.97 p3 hybrid
__has 38.55% H11 character in a s orbital

9. A bonding orbital for C4-C5 with 0.9955 electrons
__has 56.93% C 4 character in a sp2.09 hybrid
__has 43.07% C 5 character in a sp1.79 hybrid

10. A bonding orbital for C4-H8 with 0.9923 electrons
__has 60.71% C 4 character in a s0.93 p3 hybrid
__has 39.29% H 8 character in a s orbital

11. A bonding orbital for C4-H9 with 0.9914 electrons
__has 61.48% C 4 character in a s0.93 p3 hybrid
__has 38.52% H 9 character in a s orbital

12. A bonding orbital for C5-H6 with 0.9961 electrons
__has 56.06% C 5 character in a sp2.11 hybrid
__has 43.94% H 6 character in a s orbital

13. A bonding orbital for C5-H7 with 0.9960 electrons
__has 56.13% C 5 character in a sp2.11 hybrid
__has 43.87% H 7 character in a s orbital

14. A bonding orbital for C12-H13 with 0.9762 electrons
__has 63.44% C12 character in a s0.89 p3 hybrid
__has 36.56% H13 character in a s orbital

15. A bonding orbital for C12-H14 with 0.9846 electrons
__has 62.99% C12 character in a s0.96 p3 hybrid
__has 37.01% H14 character in a s orbital

16. A bonding orbital for C12-H15 with 0.9934 electrons
__has 61.84% C12 character in a sp2.95 hybrid
__has 38.16% H15 character in a s orbital

23. A lone pair orbital for O1 with 0.9895 electrons

-With core pairs on: O 1 C 2 C 3 C 4 C 5 C12 -

#### 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 C3-C4 with the lone pair acceptor orbital, 24, for C5 is 20.8 kJ/mol.

The interaction of bonding donor orbital, 6, for C3-C4 with the second antibonding acceptor orbital, 166, for O1-C2 is 38.4 kJ/mol.

The interaction of bonding donor orbital, 14, for C12-H13 with the second antibonding acceptor orbital, 166, for O1-C2 is 32.0 kJ/mol.

The interaction of lone pair donor orbital, 23, for O1 with the antibonding acceptor orbital, 169, for C2-C12 is 19.9 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.

28 ----- -2.867

27 ----- -3.134

26 ----- -4.606

25 ----- -8.317

24 -^--- -9.623

23 -^-v- -13.09

22 -^-v- -14.06

21 -^-v- -14.20

20 -^-v- -14.48

19 -^-v- -14.59

18 -^-v- -14.79

17 -^-v- -15.24

16 -^-v- -16.39

15 -^-v- -16.70

14 -^-v- -17.19

13 -^-v- -18.02

12 -^-v- -19.22

11 -^-v- -20.87

10 -^-v- -22.64

9 -^-v- -23.90

8 -^-v- -25.41

7 -^-v- -33.09

6 -^-v- -271.6
5 -^-v- -271.7
4 -^-v- -271.7

3 -^-v- -272.0

2 -^-v- -274.9

1 -^-v- -513.9

## 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 = -271.5320200892 Hartrees

Note: This ion results from the McLafferty rearrangemnt of 2-pentanone rad ical cation, CH3CH2CH2COCH3 +•. Some other conformations of this ion dissociate in calculations to ethylene and propenol radical cation, H2C=COHCH3+•. So this calculation should be considered a transient intermediate, at best. A lower energy conformer, which is closer to the McLafferty tansition state, is also available: pentenol radical cation.
* The Lewis Structure calculation (NBO analysis) was run without diffuse functions to decrease the size of the calculation.
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