Analysis

of QTAIM, IQA & FAMSEC

computational Data to attempt an
explanation for Hydrogen Bonding
phenomenon in HF adducts
A K | 2015

ABSTRACT
[Type the abstract of the document here. The abstract is typically a short
summary of the contents of the document.]


Introduction

There has been debate around the classical empirically based Chemical laws and
Interactions in molecular systems and how well they are grounded in actual physical
quantum interactions between constituent atoms and/or particles. One such a classical
chemical description is the notion of intra- and intermolecular Hydrogen bonding -
which is believed to cause lower energy of molecular systems, and a consequently
greater stability. An exact justification of this Hydrogen bond and what it is has not been
uniformly agreed upon, although an electrostatic basis has been one of the most popular
bases among scientists.

A Research paper by Pends et al. explains how using the Quantum theory of atoms in
molecules (QTAIM) in conjunction with Interacting Quantum Atoms (IQA) theory can be
used to study the interactions between atoms in molecular systems to determine
stability. 1

In this computational investigation, HF monomers and the HFHF adduct in gas phase, as
well as in simulated aqueous solvent (PCM/UFF) is subjected to Hartree Fock, basis set
6-311+G(d,p) level of theory optimization in Gaussian for QTAIM and IQA computation
using AIMStudio software. This report discusses relevant computational results,
comparing the interatomic interactions determining optimized geometry, Bond critical
point (BCP) properties and IQA energy components (as described in IQA theory by
Pends et al.) to note trends in gas phase and in solvent environments for both the HF
monomer and the HF-HF adduct dimer. In addition, FAMSEC analysis is used to
determine differences between an equilibrium inter-monomer distance adduct and one
with monomers separated by a larger distance, in an attempt to provide a physics basis
for any stability originating from the so-called Hydrogen bond.


Results & Discussion

Part 1: Comparison of Molecular Energy and Optimized Geometry of the HF
monomers and HF-HF dimers in Gas and Solvent media

Table 1: Optimized energies for HF Monomers in the two comparative media

Predicted HFHF Molecular

Medium Molecular Energy (Hartrees)
Energy (Hartrees)
Gas -100,0533 -200,1065
PCM simulated aqueous
solvent -100,0597 -200,1194

From Table 1, the HF monomer in the simulated solvent medium has a lower binding
energy, implying a greater stability.
A predicted dimer energy for either medium would be 2x the energies specified above,
assuming no stability from Hydrogen bonding to arise between molecules that will
unexpectedly lower energy.

1 Pends AM, Blanco M, Francisco E. The nature of the hydrogen bond: A synthesis from the interacting quantum atoms
picture. J.Chem.Phys. 2006;125(18):184112
Figure 1: HF Monomer equilibrium structure in Gas phase (identical for PCM)

Figure 2: HF Monomer equilibrium structure in PCM

The equilibrium structure for the HF Monomer in both the gas phase and the
PCM simulated solvent appears as in Figure 1.

The geometrical data is summarized in Table 2 below.

Table 2: Geometrical Data for HF monomers

HF Monomer Geometry data

HF Gas Selected Atoms Distances between selected atoms ()
F1 - H2 0.898
Aqueous
HF
- H2
F1
0.902
Difference () 0,005

From Table 2, it is clear that a significantly longer distance exists between the
two atoms when the monomer is in the aqueous solvent. The solvent appears to
interact with the F and H atoms separately, pulling them further apart.


The corresponding HFHF dimer data follows.

Table 3: Optimized energies for HFHF Adducts in the two comparative media

Medium Molecular Energy (Hartrees)

Gas -200.1134
PCM Solvent -200.1238

Clearly, the actual binding (molecular) energies of the HFHF adducts do indicate some
additional stabilizing, energy lowering interaction that is present in the dimer, since the
energies are lower than the predicted values in Table 1.
The traditionally expected reason for this is the Hydrogen Bonding.


Figure 3: Equilibrium adduct HFHF structure, Gasphase

Figure 4: Equilibrium adduct HFHF structure, in Simulated Solvent PCM

Table 4: Adduct geometrical properties in comparative media

Select
Distances between Distances between Magnitude of
ed
selected atoms () selected atoms () Differences ()
Atoms
HF HFHF
F1 -
HF 0,900 Solve 0,904 0,005
H2
Gas nt
F1 - F3 2,827 2,747 0,080

F1 -
1,935 1,841 0,094
H4
H2 -
3,435 3,360 0,075
F3
H2 -
2,600 2,477 0,124
H4
F3 -
0,901 0,906 0,005
H4

HF Select HFHF Magnitude of
Angles between Angles between
HF ed Solve Differences
atoms (degrees) atoms (degrees)
Gas Atoms nt (degrees)
F1 -
H2 - 41,6746 41,3780 0,296585

F3
H2 -
126,1049 126,0505 0,054377
F1 - F3
F1 - F3
12,2205 12,5715 0,350963
- H2
F1 -
H2 - 35,1725 37,3440 2,17154

H4
H2 -
F1 - 129,2894 125,3185 3,970938

H4
F1 -
H4 - 15,5381 17,3375 1,799398

H2
F1 - F3
6,8523 1,4873 5,364944
- H4
F3 - F1
3,1845 0,7320 2,452536
- H4
F1 -
H4 - 169,9632 177,7807 7,817479

F3
H2 -
F3 - 19,0728 11,0842 7,988614

H4
 F3 -
H2 - 6,5022 4,0340 2,468126

H4
H2 -
H4 - 154,4251 164,8818 10,456739

F3

HF Select Dihedral angle HFHF Dihedral angle Magnitude of
HF ed between selected Solve between selected Differences
Gas Atoms atoms (degrees) nt atoms (degrees) (degrees)
F1 -
H2 -
0,0000 0,0000 0
F3 -
H4
F1 -
H2 -
-180,0000 180,0000 360
H4 -
F3
F1 -
H4 -
0,0000 180,0000 180
F3 -
H2
H2 -
F1 - F3 -180,0000 0,0000 180

- H4
H2 -
F1 -
0,0000 180,0000 180
H4 -
F3
F3 - F1
- H2 - 0,0000 0,0000 0

H4


There are significant differences between the interatomic distances in the gas phase and
in aqueous phase.












 Part 2: Comparison of QTAIM Bond Critical Point computed data for the Monomers
and Adducts in Gas phase and Aqueous phase


Figure 5: Molecular Graph of HF Monomer in Gasphase

Figure 6: Molecular Graph of HF Monomer in PCM simulated solvent

The molecular graphs for the two monomers appear similar in terms of bonding
interactions.

Table 5: Bond Critical Point Topological Properties for the HF monomer

DelSqRho
Delocalization
Atoms Rho () (Laplacian of local V local G |V|/G
Index (A|B)
Rho)

Gas F1 - H2 0,3960 -3,4206 -1,0245 0,0847 12,0970 0,4404

Solvent
(PCM) F1 - H2 0,3858 -3,4212 -1,0123 0,0785 12,8925 0,4071
V is the local Potential Energy density of the Indicated BCP
G is the Local Kinetic Energy density of the indicated BCP

From the data in Table 5, it can be seen that the Laplacian of is negative, which
is expected for covalent bond interactions, as is expected here. In solvent, the
bond appears to be slightly more covalent, although according to the electron
density of the BCP, the gas phase monomer has a stronger HF bond. This explains
why the bond length in solvent is longer than the one in gas phase.

Figure 7: Molecular Graph of HFHF equilibrium Adduct in Gasphase

Figure 8: Molecular Graph of HFHF equilibrium Adduct in simulated PCM solvent

From the molecular graphs of the two dimers, the one in simulated solvent
appears to have a greater distance between the two monomers, which agrees
with the general trend identified for HF above, where solvent monomer or
solvent-atom interactions cause a greater distance in bonding interaction, and
equivalently, a smaller electron density/bond strength.

















Table 6: Bond Critical Point Topological Properties for the HFHF adduct

DelSqRho
Delocalization
Atoms Rho () (Laplacian of local V local G |V|/G
Index (A|B)
Rho)
-
Gas F1 - H4 0,015821 0,088216 0,014251 0,018152 0,7851 0,029772
-
F1 - H2 0,388855 -3,418265 1,015086 0,08026 12,6475 0,416379
-
F3 - H4 0,387844 -3,435125 1,020882 0,08105 12,5957 0,383231


Solvent
(PCM) F1 - H4 0,020013 0,111471 -0,01931 0,023589 0,8186 0,037569

F1 - H2 0,378474 -3,406999 -1,00064 0,074445 13,4413 0,38688
-
F3 - H4 0,376744 -3,395461 1,001923 0,076529 13,0921 0,353926

From Table 6, the bond path between F1 and H4 is not covalent in character,
since the Laplacian of that BCP is Positive. This indicates that it is not a
traditional bond as for the Monomer HF bonds, but instead is a bonding
interaction nonetheless. This hydrogen bond is an open shell interaction. Again,
the fact that the ratio of local Potential energy to local kinetic energy is less than
1, also reinforces the identity of the F1-H4 interaction as open shell.

The value of also indicates that there is less electron density present in this
open shell interaction.
In the solvent, the interaction is stronger, which suggests that the aqueous
solvent reinforces this Hydrogen bonding interaction between the two
monomers, whilst at the same time, as seen for the monomers in solvent, the
covalent bonds intra to the monomers are weaker, and the bond lengths longer.

The delocalization indices of the bond paths also show that in gas phase, the
covalent bonds are stronger with a greater magnitude of electron pairs
delocalized between the atoms than when the adduct is in solvent.

Hence, the solvent increases the magnitude of the open shell Hydrogen bonding,
even as it decreases the strength of the covalent bonds of the monomers.


Part 3: Comparison of IQA computed energies for the atoms in the Monomers and
Adducts in Gas phase and Aqueous phase


Below follows a Table with the IQA energies described above, for the Monomers:


 Table 7: IQA Additive and Self energies of monomers in gas phase and in solvent

A A
E_IQA Difference in Difference
t E_IQA( Solv t E_IQA_Intra
Gas _Intra E_IQA(A) Additive in Self
o A) ent o (A)
(A) energies Energies
m m

- -
F F -
9,96E+ 9,94E -9,94E+01 -6,6249E-03 -3,2694E-03
1 1 9,96E+01
01 +01
-
H -4,33E- H -4,26E-
1,95E- -1,84E-01 7,1235E-03 1,1114E-02
2 01 2 01
01

T T
- -
o o -
1,00E+ 9,96E -9,96E+01 4,9857E-04 7,8442E-03
t ta 1,00E+02
02 +01
al l

E_IQA(A) is the additive energy for specified atom.
E_IQA_Intra is the self energy of the specified atom. All values are in a.u.


Clearly, from Table 7, the additive energy of the Hydrogen is less in solvent than
in gas phase, which suggests that it is the atom involved in interaction with the
aqueous medium. The additive energies of the F atoms are different to a lesser
extent.

The self energies also only differ significantly for the Hydrogen atom between
the two phases.


Table 8: Diatomic Interaction Energies for the Monomers in both phases

Atom A Atom B E_IQA_Inter(A,B)

Gas H2 F1 -4,75E-01


Solvent H2 F1 -4,83E-01
Difference in
diatomic -8,00E-03

interaction
energies








For the adducts, a similar comparison is made:

Table 9: IQA Additive and Self energies of adducts in gas phase and in solvent

At At
G Sol Difference in
o E_IQA E_IQA_I o E_IQA E_IQA_I Difference in
a ven Additive
m (A) ntra(A) m (A) ntra(A) Self Energies
s t energies
(A) (A)
- - - -
F1 9,963 9,9377E F1 9,964 9,9379E -8,4017E-03 -1,7220E-03

9E+01 +01 7E+01 +01
- - - -
H2 4,171 1,8768E H2 4,079 1,7769E 9,1752E-03 9,9966E-03

7E-01 -01 9E-01 -01
- - - -
F3 9,961 9,9381E F3 9,962 9,9382E -3,8446E-03 -1,1483E-03

8E+01 +01 2E+01 +01
- - - -
H4 4,390 1,8358E H4 4,348 1,7493E 4,1964E-03 8,6494E-03

4E-01 -01 4E-01 -01

- - - -
To To
2,001 1,9913E 2,001 1,9911E 1,1253E-03 1,5776E-02
tal tal
1E+02 +02 1E+02 +02

All values in Table 9 above are in a.u.
E_IQA(A) is the additive energy for specified atom.
E_IQA_Intra is the self energy of the specified atom. All values are in a.u.


For the dimers, we notice that now the Hydrogen atoms all have lower additive
energies in the solvent phase (most likely due to Hydrogen bonding with the
Aqueous solvent), whereas the Fluorine atoms also all have lower additive
energies in the solvent phase. This is the reason for the molecules lower energy
in solvent than in free gas phase, viz. part I above.

The self energies for the F atoms in solvent are higher however, whereas the
Hydrogen atoms all have a lower self energy in solvent. Therefore, it is concluded
that the Hydrogen stabilization is the main cause of the adduct being more stable
in aqueous medium.










Table 10: Diatomic Interaction Energies (E_IQA_INTER(A,B) for the Adducts in both phases

Atom A Atom B E_IQA_Inter(A,B) Differences in E_IQA_Inter(A,B)

Gas
H2 F1 -4,7987E-01
F3 F1 1,0637E-01
F3 H2 -9,9440E-02
H4 F1 -1,4878E-01
H4 H2 1,2034E-01
H4 F3 -4,8249E-01

Solvent H2 F1 -4,8566E-01 -5,7876E-03
F3 F1 1,1285E-01 6,4873E-03
F3 H2 -1,0627E-01 -6,8264E-03
H4 F1 -1,6377E-01 -1,4993E-02
H4 H2 1,3128E-01 1,0940E-02
H4 F3 -4,8731E-01 -4,8113E-03

From this table, it appears as though the hydrogen open shell bonding
interaction occurs more stable in the solvent, due to the lower diatomic
interaction energy. In gas phase, the covalent bonds are also not as stable as in
aqueous medium, having higher energy values.

Part 4: Seeing the effect of an increased distance between monomers in an adduct,
in gas phase

Now will follow comparisons of the Energies of the equilibrium adduct in gas
phase with the Adduct when it has a fixed distance of 3 Angstrom between the
two F atoms in the constituting monomers of a gas phase adduct:

At first, the adduct with 3 distance between F atoms was only subjected to a
single point energy calculation (SPC), and afterward to an Optimization
calculation to allow monomers to rotate relative to one another.

Figure 9: SPC HFHF Gas adduct, subjected only to SPC calculation

Figure 10:Optimization HFHF gas adduct , subjected to optimization


QTAIM analysis of BCP data:

DelSqRh DI(A|B
OPT 3A structure Atoms Rho o G V |V|/G )

F1 - 0,388 - 12,647
H2 9 -3,4183 0,0803 1,0151 5 0,4164
F1 - 0,015 -
H4 8 0,0882 0,0182 0,0143 0,7851 0,0298
F3 - 0,387 - 12,595
H4 8 -3,4351 0,0811 1,0209 7 0,3832


Equilibrium -
F1 0,015 -
adduct H4 8 0,0882 0,0143 0,0182 0,7851 0,0298
F1 - 0,388 - 12,647
H2 9 -3,4183 1,0151 0,0803 5 0,4164
F3 - 0,387 - 12,595
H4 8 -3,4351 1,0209 0,0811 7 0,3832

From this BCP data, we see that the hydrogen bond interaction between F1 and
H4 is still open shell interaction, and we note that at the increased distance, there
is still the same amount of electron density in the bond, as well as in the other
intramonomer covalent bonds (as expected). The optimization allows the dimer
to arrange so as to attain the equilibrium structure electron delocalization, which
was not so in the SPC calculation.



Table 11: IQA Energy Comaprisons between Optimized HFHF adduct with 3Angstrom
distance between F atoms, and equilibrium HFHF adduct, gasphase

Equl A E_I E_I Addu A E_I E_I E_I
ibriu t QA QA_ ct 3 t QA QA_ E_ QA_ E_IQ
m o E_I _Int Inte Angst o E_I _Int Inte IQ INT A_IN
Add m QA ra( r(A, rom m QA ra( r(A, A( RA( TER(
uct (A) A)
B) OPT (A) A)
B) A) A) A,B)
- -
9,9 - 9,9 - 2,
63 9,9 63 9,9 95
9E 377 9E 377 30 1,32
F +0 E+0 F +0 E+0 E- 93E-
1 1 1 1 1 1 06 04
- - - - - -
4,1 1,8 4,1 1,8 5, 6,44
H 71 768 H 71 769 43 11E-
2 7E E- 2 7E E- 64 06

 - 01 - 01 E-
01 01 06
- - -
9,9 - 9,9 - 8,
61 9,9 61 9,9 38
8E 381 8E 381 00 1,50
F +0 E+0 F +0 E+0 E- 81E-
3 1 1 3 1 1 07 04
- -
4,3 - 4,3 - 2,
90 1,8 90 1,8 96
4E 358 1E 354 68 4,56
H - E- H - E- E- 50E-
4 01 01 4 01 01 05 05

- -
2,0 - 2,0 - 2,
T 01 1,9 T 01 1,9 63
o 1E 913 o 1E 913 50 3,22
t +0 E+0 t +0 E+0 E- 95E-
al 2 2 al 2 2 05 04


A
A
t A t A
o t o t
m o m o
m m
A B A B

- -
4,79 4,79 1,11
H F 87E H F 87E 46E-
2 1 -01 2 1 -01 06
-
1,06 1,06 2,19
F F 37E F F 37E 65E-
3 1 -01 3 1 -01 07
- - -
9,94 9,94 2,52
F H 40E F H 40E 50E-
3 2 -02 3 2 -02 08
- -
1,48 1,48 1,78
H F 78E H F 76E 47E-
4 1 -01 4 1 -01 05
H 1,20 H 1,20 -
4 H 34E 4 H 32E 2,37

 2 -01 2 -01 09E-
05
- -
4,82 4,82 9,41
H F 49E H F 49E 36E-
4 3 -01 4 3 -01 07




Table with BCP data for SPC vs Equilibrium structure BCP data
DelSqRh DI(A|B
SPC 3A structure Atoms Rho o G V |V|/G )

-
F1 0,389 - 0,080 12,544
H2 6 -3,4104 1,0143 9 2 0,4208
F1 - 0,010 - 0,010
H4 3 0,0555 0,0080 9 0,7288 0,0207
F3 - 0,388 - 0,081 12,542
H4 7 -3,4161 1,0160 0 6 0,3969


Equilibrium -
F1 0,015 - 0,018
adduct H4 8 0,0882 0,0143 2 0,7851 0,0298
F1 - 0,388 - 0,080 12,647
H2 9 -3,4183 1,0151 3 5 0,4164
F3 - 0,387 - 0,081 12,595
H4 8 -3,4351 1,0209 1 7 0,3832

Clearly, the marked differences prior to allowing the molecule to orientate itself
to reach the desired electron delocalization , leads to very different electron
density values, and DI values, as opposed to the Similarities encountered for the
optimized 3 Angstrom structure.

Table 12: IQA Energy Comaprisons between SPC HFHF adduct with 3Angstrom distance
between F atoms, and equilibrium HFHF adduct, gasphase

Equl A E_I E_I Addu A E_I E_I E_IQ
ibri t E_ QA QA ct 3 t E_IQ QA_ E_ QA_ A_I
um o IQ _In _Int Angs o A_In Inte IQ INT NTE
Add m A( tra( er( trom m E_IQ tra( r(A, A( RA( R(A,
uct A) A) A,B) SPC A(A) A)
B) A) A) B)
- - -
9, - 9.96 9.93 9,
96 9,9 364 792 96 9,9
39 377 804 732 39 377
F E+ E+0 F 39E 23E E+ E+0
1 01 1 1 +01 +01 01 1

 - - -
4, - 4.19 1.89 4,
17 1,8 272 021 17 1,8
17 768 283 542 17 768
H E- E- H 08E- 01E- E- E-
2 01 01 2 01 01 01 01
- - -
9, - 9.96 9.93 9,
96 9,9 183 818 96 9,9
18 381 135 014 18 381
F E+ E+0 F 82E 94E E+ E+0
3 01 1 3 +01 +01 01 1
- - -
4, - 4.38 1.86 4,
39 1,8 959 493 39 1,8
04 358 332 118 04 358
H E- E- H 78E- 12E- E- E-
4 01 01 4 01 01 01 01

- - -
2, - 2.00 1.99 2,
T 00 1,9 T 113 136 00 1,9
o 11 913 o 025 589 11 913
t E+ E+0 t 64E 38E E+ E+0
al 02 2 al +02 +02 02 2


A A A A
t t t t
o o o o
m m m m

A B A B

-
- 4.79
4,7 199
987 755 4,79
H F E- H F 50E- 87E-
2 1 01 2 1 01 01

1.01
1,0 803 -
637 968 1,06
F F E- F F 74E- 37E-
3 1 01 3 1 01 01
F - F - 9,94

 3 H 9,9 3 H 9.35 40E-
2 440 2 014 02
E- 221
02 36E-
02
-
- 1.36
1,4 375
878 811 1,48
H F E- H F 03E- 78E-
4 1 01 4 1 01 01

1.12
1,2 200 -
034 221 1,20
H H E- H H 15E- 34E-
4 2 01 4 2 01 01
-
- 4.80
4,8 743
249 688 4,82
H F E- H F 58E- 49E-
4 3 01 4 3 01 01