Supplementary Information
Step-by-step DFT analysis of the cooperativity in the binding
of cations and anions to a tetratopic ion-pairing host
Ethan N. W. Howe,a,b Graham E. Ball,a and Pall Thordarsona,b*
a
School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia.
b
Australian Centre for Nanomedicine and the ARC Centre of Excellence in Convergent Bio-Nano
Science and Technology, The University of New South Wales, Sydney, NSW 2052, Australia.
* To whom correspondence should be addressed.
Email: p.thordarson@unsw.edu.au
Contents
1.
Details of computational methods ........................................................................................... 2
2.
Computational results summary .............................................................................................. 6
3.
Coordinates of optimised geometry and frequency calculation summary using DFT at
PBE1PBE/6-31+G(d)............................................................................................................... 9
4.
Infrared spectra from vibrational frequency calculations at PBE1PBE/6-31+G(d) .............. 26
5.
Summary of computed energies for ∆E calculations ............................................................. 33
6.
References .............................................................................................................................. 37
1
1.
Details of computational methods
Software
DFT calculations were performed using the Gaussian 09 software package,1 revision B.01 for
geometry optimisation, revision D.01 for single point energy, frequency, and counterpoise
correction calculations, running on 8-core Mac-Pro workstations and the Fujitsu cluster of the
Australian National Computing Infrastructure National Facility.
When necessary, preliminary energy minimisations using the MM2 force field method were
performed using the ChemBioOffice Ultra 2010 Suite software package,2 ChemBio3D Ultra
version 12.0, running on an Intel Quad-Core CPU at 3.50 GHz with 8 GB of RAM on a
Windows 7 64-bit operating system.
The molecular graphics were generated using the PyMOL Molecular Graphics System3 and
Mercury4 software packages. The infrared spectra from the vibrational frequency calculations
were generated using the Gabedit5 software, the infrared spectra line-shapes were convoluted
using Lorentzian functions with a half-width at a half-maximum of 20 cm−1.
Methodology
All DFT calculations were performed using the default spin restricted closed shell
wavefunctions. Calculations were performed on the free host and host‒guest complexes in
vacuum unless otherwise stated and the default “fine” integration grid implemented in the
Gaussian 09 software was employed throughout unless otherwise stated. Where calculations in
2
solvent are indicated, the self-consistent reaction field (SCRF) method, with the polarised
continuum model (PCM)6,
7
method employing chloroform as solvent was implemented in
Gaussian 09.
For geometry optimisations and frequency calculations of the free host and host‒guest
complexes, the hybrid PBE08 functional, PBE1PBE/6-31+G(d)9,
polarisation and diffuse functions11,
12
10
level of theory, with
was employed for all heavy elements. All geometry
optimisations were performed using the default Berny optimisation algorithm (GEDIIS)13 with
the default cut-offs employed, unless otherwise stated. All optimised geometries in vacuum
converged to average RMS forces on all atoms within less than 9.2 × 10−6 a.u.; optimised
geometries in chloroform (PCM) solvent environment converged to average RMS forces on all
atoms within less than 1.8 × 10−5 a.u. All minimum energy structures for the free host and host‒
guest complexes were calculated without any symmetry constraints and were confirmed to be
minima by calculating their normal vibrations within the harmonic approximation and observing
that there were no imaginary frequencies. Geometry optimisations for minimised structures that
showed negative frequencies were repeated using “tight” convergence criteria with the
“ultrafine” integration grid implemented in Gaussian 09; this resulted in minimised structures
which were negligibly different in geometry and energy with no imaginary frequencies. See
Table S1 for the computational result summary.
The input starting geometry for the quantum mechanical DFT geometry optimisation of the free
host (H) was performed from the X‒ray crystal structure (CCDC#994170, available from the
Cambridge Structural Database). The input geometry of the H•Cl− complex was generated by
taking the X‒ray crystal structure of H and docking a chloride atom at the centre of the
centrosymmetric host; similarly the H•2Cl− ternary complex was created from the X‒ray crystal
3
structure of H by adding two chloride atoms each at the isophthalamide anion binding sites, in
the plane of the aromatic ring.
From our previously reported cation NMR binding study results,14 it was apparent that the
binding towards calcium cation induced significant structural perturbation to the folded-closed
conformation of macrocyclic host, resulting in two different conformations for the 1:1 and 1:2
host‒guest calcium cation complexes. As was described previously,14 the initial input
coordinates for H•Ca2+ complex was constructed by docking one calcium atom at the centre of
the X‒ray crystal structure of H. This structure was preliminarily minimised using the MM2
force field method with either ten dummy bonds between the calcium atom and all the oxygen
atoms, or with six dummy bonds between the calcium atom and the crown-6 oxygen atoms. The
dummy bonds were removed from the two MM2 minimised structures and these were then used
as input geometries for DFT geometry optimisation. Both input structures were fully optimised
and the latter was computed with a lower total energy.
The initial structure for the H•2Ca2+ complex was taken from the X‒ray crystal structure of
H•2[Ca(ClO4)2]•4H2O complex (CCDC#994171, available from the Cambridge Structural
Database), and the four counter-anions and four axial water ligands were removed before
performing DFT geometry optimisation. Lastly, the input coordinates for the 2Ca2+•H•2Cl−
quinary complex was obtained by taking the DFT minimised structures of H•2Ca2+ and adding
two chloride atoms each at the isophthalamide anion binding sites, in the plane of the aromatic
ring. See Section 3.1−3.10 below for the parameters and coordinates for all fully optimised
structures.
4
Single point energy calculations for all the fully optimised structures were performed with the
larger basis set, with polarisation and diffuse functions for both hydrogen and heavy atoms at the
PBE1PBE/6-311++G(d,p) level of theory. The computed energies used in the calculation of
binding energy for all host‒guest systems in vacuum were corrected for the basis set
superposition error (BSSE) using the counterpoise (CP)15 method implemented in Gaussian 09.
In addition, the calculated BSSE energies in vacuum were used to implement CP corrections for
the calculated energies in chloroform (PCM) solvent environment.
Additional single point energy calculations for optimised structures of free host, H•Cl‒ and
H•Ca2+ complexes were performed with a large 6-311++G(2df,2p) basis set using the hybrid
functionals PBE1PBE,8 B3LYP16 and M06,17 and the dispersion-corrected density functionals
B3LYP-GD3BJ18 and ωB97X-D.19 The chloroform solvent environment was applied in these
calculations using a universal continuum solvation model (SMD).20 The computed energies used
in the calculation of binding energy were CP corrected using BSSE energies obtained from
calculation at the PBE1PBE/6-311++G(2df,2p) level of theory. Details on the computed energies
for ∆E arithmetic calculations are given in Section 4 below.
5
2.
Computational results summary
Table S1. Energy, dipole moment, point group and RMS gradient data of free host and host‒
guest complexes in vacuum and chloroform (PCM), computed from the geometry optimisations
and frequency calculation at PBE1PBE/6-31+G(d) level of theory.
species in vacuum
and chloroform
free host (H)
H•Cl
−
H•2Cl
H•Ca
−
2+
H•2Ca
2+
2Ca2+•H•2Cl−
a
overall
charge
point
group
Gibbs free
energya (a.u.)
dipole
(debye)
imaginary
frequencies
RMS
grad. norm.
vacuum
0
C1
‒2371.01814
0
0
9.14 × 10‒6
chloroform
0
C1
‒2371.04238
0
0
5.66 × 10‒6
vacuum
‒1
C1
‒2831.18643
0
0
4.10 × 10‒7
chloroform
‒1
C1
‒2831.24986
1.4454
0
2.74 × 10‒6
vacuum
‒2
C1
‒3291.27775
0.0015
0
1.99 × 10‒6
chloroform
‒2
C1
‒3291.44096
0.2346
0
4.57 × 10‒6
vacuum
2
C1
‒3048.07656
0.0005
0
2.39 × 10‒6
chloroform
2
C1
‒3048.24190
2.0749
0
1.31 × 10‒5
vacuum
4
C1
‒3724.89298
0.0021
0
3.15 × 10‒6
chloroform
4
C1
‒3725.41894
0.0104
0
1.75 × 10‒5
vacuum
2
C1
‒4645.75791
0.0040
0
4.04 × 10‒6
chloroform
2
C1
‒4645.95794
1.2754
0
4.74 × 10‒6
Gibbs free energy reported in Hartrees (a.u.) from the sum of total electronic and thermal free energies,
computed at 298.15 K and 1.00 atm, with zero-point and thermal correction included.
6
Table S2. Zero point vibrational energy corrections (unscaled) from frequency calculations at the
PBE1PBE/6-31+G(d) level of theory.
Species
Phase
Zero point vibrational
energy correction
(Hartree)
Zero point vibrational
energy correction
(kcal mol-1)
vacuum
0.879827
552.10
chloroform
0.879568
551.94
vacuum
0.879147
551.67
chloroform
0.879219
551.72
vacuum
0.879274
551.75
chloroform
0.880498
552.52
vacuum
0.884898
555.28
chloroform
0.891067
559.15
vacuum
0.888628
557.62
chloroform
0.894326
561.20
vacuum
0.888590
557.60
chloroform
0.892216
559.87
Free Host
H-Cl complex
H-Cl2 complex
H-Ca complex
H-Ca2 complex
H-Ca2Cl2 complex
7
Table S3. Corrections from frequency calculations (PBE1PBE/6-31+G(d)) applied to calculating
the ∆Ebinding (PBE1PBE/6-311++G(d,p)// PBE1PBE/6-31+G(d)).
ZPVE correction
to ∆Ebinding
(kcal mol-1)
∆Ebinding without
ZPVE correction
(kcal mol-1)
∆Ebinding plus
ZPVE correction
(kcal mol-1)
vacuum
-0.43
-37.64
-38.07
CHCl3
-0.22
-6.94
-7.16
vacuum
0.08
9.33
9.41
CHCl3
0.80
-0.27
0.53
vacuum
-0.35
-28.31
-28.66
CHCl3
0.58
-7.21
-6.63
vacuum
3.18
-251.45
-248.27
CHCl3
7.22
-66.62
-59.40
vacuum
2.34
-96.71
-94.37
CHCl3
2.05
-41.54
-39.49
vacuum
5.52
-348.16
-342.64
CHCl3
9.26
-108.16
-98.90
vacuum
-0.02
-418.79
-418.81
CHCl3
-1.32
-95.03
-96.35
vacuum
5.85
-738.64
-732.79
CHCl3
7.35
-195.99
-188.64
vacuum
5.50
-766.95
-761.45
CHCl3
7.94
-203.19
-195.25
host‒guest reaction
H + Cl−
[Cl−•H] + Cl−
H + 2Cl−a
H + Ca2+
[Ca2+•H] + Ca2+
H + 2Ca2+a
[2Ca2+•H] + 2Cl−a
[2Cl−•H] + 2Ca2+a
H + 2Ca2+ + 2Cl−b
a
Coincidental three component binding.
b
Coincidental five component binding.
8
3.
Coordinates of optimised geometry and frequency calculation summary using DFT at
PBE1PBE/6-31+G(d)
3.1
Free host in vacuum
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒2371.809144 a.u.
Zero-point correction: 0.879827 a.u.
Thermal correction to energy: 0.930231 a.u.
Thermal correction to enthalpy: 0.931175 a.u.
Thermal correction to Gibbs free energy: 0.791003 a.u.
O
O
N
H
N
H
C
H
C
C
H
C
H
C
H
C
C
C
O
O
O
C
H
H
C
H
H
C
H
H
0.261878
-1.971653
-1.307754
-1.458759
-0.462537
-0.137577
0.685405
-0.345384
0.990148
2.319758
2.548063
3.319840
4.349558
3.006743
3.773361
1.689319
-0.051185
-1.392472
-2.450927
0.339421
1.660462
-2.464061
-2.121486
-3.164754
-3.173207
-3.332539
-4.163524
-2.416142
-1.380919
-2.892869
2.526565
1.548772
2.020612
1.751164
2.326414
2.223727
0.294376
-0.035088
1.344194
1.749660
2.539469
1.155893
1.489638
0.134695
-0.331716
-0.318800
2.026788
1.446704
5.400857
6.341414
4.915407
2.509798
2.833859
1.675479
3.653524
3.381901
3.795558
4.964004
4.838984
5.722170
5.008006
0.567275
3.427907
2.457591
-0.951194
-1.902732
2.211471
2.104245
3.080761
3.215382
3.923995
2.450346
2.551044
1.557481
0.944750
1.455826
3.928177
-0.518845
4.849595
3.868423
1.703630
4.154011
5.139687
4.295238
3.430340
2.378430
3.882145
3.501843
3.159451
2.857542
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
O
O
N
H
N
H
C
H
C
-1.687700
-2.018173
-1.907271
-0.190175
0.286813
0.008537
1.701997
1.863687
2.295205
2.177726
1.852188
3.281248
2.005590
3.100867
1.568269
1.501405
1.981561
1.814067
-0.013037
-0.329023
-0.508887
-0.261878
1.971653
1.307754
1.458759
0.462537
0.137577
-0.685405
0.345384
-0.990148
6.547482
6.876780
7.353992
6.309410
7.097008
5.334408
6.004075
5.004560
6.730552
6.027186
6.965212
6.001387
4.915689
4.982132
5.799171
3.638601
2.772704
3.650841
3.489994
3.370549
4.391803
-2.526565
-1.548772
-2.020612
-1.751164
-2.326414
-2.2237270
-0.294376
0.035088
-1.344194
5.132733
6.124146
4.413075
5.178202
5.788948
5.649089
3.826381
4.259352
4.409851
2.395338
1.916465
2.379131
0.340575
0.223697
-0.158627
-0.303130
0.167712
-1.357697
-0.212794
0.824627
-0.601976
-5.008006
-0.567275
-3.427907
-2.457591
0.951194
1.902732
-2.211471
-2.104245
-3.080761
9
C
H
C
H
C
H
C
C
C
O
O
O
C
H
H
C
H
H
C
H
H
3.2
-2.319758
-2.548063
-3.319840
-4.349558
-3.006743
-3.773361
-1.689319
0.051185
1.392472
2.450927
-0.339421
-1.660462
2.464061
2.121486
3.164754
3.173207
3.332539
4.163524
2.416142
1.380919
2.892869
-1.749660
-2.539469
-1.155893
-1.489638
-0.134695
0.331716
0.318800
-2.026788
-1.446704
-5.400857
-6.341414
-4.915407
-2.509798
-2.833859
-1.675479
-3.653524
-3.381901
-3.795558
-4.964004
-4.838984
-5.722170
-3.215382
-3.923995
-2.450346
-2.551044
-1.557481
-0.944750
-1.455826
-3.928177
0.518845
-4.849595
-3.868423
-1.703630
-4.154011
-5.139687
-4.295238
-3.430340
-2.378430
-3.882145
-3.501843
-3.159451
-2.857542
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
1.687700
2.018173
1.907271
0.190175
-0.286813
-0.008537
-1.701997
-1.863687
-2.295205
-2.177726
-1.852188
-3.281248
-2.005590
-3.100867
-1.568269
-1.501405
-1.981561
-1.814067
0.013037
0.329023
0.508887
-6.547482
-6.876780
-7.353992
-6.309410
-7.097008
-5.334408
-6.004075
-5.004560
-6.730552
-6.027186
-6.965212
-6.001387
-4.915689
-4.982132
-5.799171
-3.638601
-2.772704
-3.650841
-3.489994
-3.370549
-4.391803
-5.132733
-6.124146
-4.413075
-5.178202
-5.788948
-5.649089
-3.826381
-4.259352
-4.409851
-2.395338
-1.916465
-2.379131
-0.340575
-0.223697
0.158627
0.303130
-0.167712
1.357697
0.212794
-0.824627
0.601976
1.449073
0.050297
-0.394395
-0.440566
1.816300
1.580186
5.266182
6.441255
5.184113
2.452126
2.645354
1.670320
2.598675
1.611798
1.005611
1.504518
3.990854
-0.569347
4.987471
3.879355
1.628792
4.086517
5.124503
4.081894
Free host in chloroform (PCM) solvent environment
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒2371.833831 a.u.
Zero-point correction: 0.879568 a.u.
Thermal correction to energy: 0.929895 a.u.
Thermal correction to enthalpy: 0.930839 a.u.
Thermal correction to Gibbs free energy: 0.791447 a.u.
O
O
N
H
N
H
C
H
C
C
H
C
0.004786
-1.929174
-1.451004
-1.536074
-0.370526
-0.020741
0.544904
-0.478302
0.824067
2.140033
2.352583
3.155593
2.155243
1.688271
1.948164
1.775104
2.460588
2.370077
0.145232
-0.206834
1.192829
1.641302
2.438331
1.082168
5.151874
0.496154
3.404187
2.402841
-0.972045
-1.916728
2.257224
2.151070
3.137395
3.273637
3.979926
2.502368
H
C
H
C
C
C
O
O
O
C
H
H
4.174019
2.871175
3.655399
1.567174
-0.244183
-1.307437
-2.264944
0.372248
1.695163
-2.627470
-2.347590
-3.398306
10
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
O
O
N
H
N
H
C
H
C
C
H
C
3.3
-3.184076
-3.339746
-4.168514
-2.295388
-1.281534
-2.698907
-1.561383
-1.832549
-1.899411
-0.051684
0.400722
0.268987
1.765836
2.102548
2.288425
2.130952
1.669349
3.225349
1.970238
3.050077
1.446309
1.525481
2.073771
1.803339
0.026544
-0.252137
-0.532176
-0.004786
1.929174
1.451004
1.536074
0.370526
0.020741
-0.544904
0.478302
-0.824067
-2.140033
-2.352583
-3.155593
3.717819
3.542519
3.929597
4.932789
4.734803
5.782943
6.445800
6.677625
7.279548
6.332466
7.140510
5.368751
6.301367
5.344757
7.114751
6.358521
7.245376
6.458499
5.196035
5.338701
6.041331
3.883371
3.053096
3.905689
3.643315
3.495703
4.516143
-2.155243
-1.688271
-1.948164
-1.775104
-2.460588
-2.370077
-0.145232
0.206834
-1.192829
-1.641302
-2.438331
-1.082168
3.437203
2.364566
3.874100
3.608857
3.237624
3.034834
5.303542
6.339090
4.666131
5.222494
5.823156
5.648498
3.736244
4.166442
4.267453
2.274748
1.811347
2.182819
0.245665
0.076025
-0.233101
-0.367782
0.093794
-1.430937
-0.231884
0.812674
-0.600223
-5.151874
-0.496154
-3.404187
-2.402841
0.972045
1.916728
-2.257224
-2.151075
-3.137395
-3.273637
-3.979926
-2.502368
H
C
H
C
C
C
O
O
O
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
-4.174019
-2.871175
-3.655399
-1.567174
0.244183
1.307437
2.264944
-0.372248
-1.695163
2.627470
2.347590
3.398306
3.184076
3.339746
4.168514
2.295388
1.281534
2.698907
1.561383
1.832549
1.899411
0.051684
-0.400722
-0.268987
-1.765836
-2.102548
-2.288425
-2.130952
-1.669349
-3.225349
-1.970238
-3.050077
-1.446309
-1.525481
-2.073771
-1.803339
-0.026544
0.252137
0.532176
-1.449073
-0.050297
0.394395
0.440566
-1.816300
-1.580186
-5.266182
-6.441255
-5.184113
-2.452126
-2.645354
-1.670320
-3.717819
-3.542519
-3.929597
-4.932789
-4.734803
-5.782943
-6.445800
-6.677625
-7.279548
-6.332466
-7.140510
-5.368751
-6.301367
-5.344757
-7.114751
-6.358521
-7.245376
-6.458499
-5.196035
-5.338701
-6.041331
-3.883371
-3.053096
-3.905689
-3.643315
-3.495703
-4.516143
-2.598675
-1.611798
-1.005611
-1.504518
-3.990854
0.569347
-4.987471
-3.879355
-1.628792
-4.086517
-5.124503
-4.081894
-3.437203
-2.364566
-3.874100
-3.608857
-3.237624
-3.034834
-5.303542
-6.339090
-4.666131
-5.222494
-5.823156
-5.648498
-3.736244
-4.166442
-4.267453
-2.274748
-1.811347
-2.182819
-0.245665
-0.076025
0.233101
0.367782
-0.093794
1.430937
0.231884
-0.812674
0.600223
H•Cl− complex in vacuum
Optimisation parameters: Tight cut-off, ultrafine integration grid
Spin: Singlet
Energy: ‒2831.969018 a.u.
11
Zero-point correction: 0.879147 a.u.
Thermal correction to energy: 0. 0.931911 a.u.
Thermal correction to enthalpy: 0.932855 a.u.
Thermal correction to Gibbs free energy: 0.782586 a.u.
Cl
O
O
N
N
C
C
C
C
C
C
C
C
O
O
O
C
C
C
C
C
C
C
C
C
C
O
O
N
N
C
C
C
C
C
C
C
C
O
O
O
0.000022
4.724399
1.647132
2.972998
1.561344
1.277840
2.643730
3.176059
2.344057
0.980430
0.437404
3.551113
1.023987
6.295240
7.170416
4.867102
3.523828
3.968596
5.242270
7.536241
7.541686
6.769591
6.117911
4.242147
2.864830
2.897470
-4.724357
-1.647094
-2.972954
-1.561303
-1.277799
-2.643689
-3.176019
-2.344018
-0.980392
-0.437364
-3.551071
-1.023947
-6.295195
-7.170375
-4.867061
-0.000002
-2.574853
5.097015
-1.173828
2.897271
-3.124990
-3.045883
-3.814816
-4.636789
-4.713149
-3.944327
-2.237337
4.042456
0.460669
0.350912
0.979410
-0.539911
0.908576
1.038395
0.391360
-0.459829
-0.363084
0.600681
2.001553
2.261519
2.802853
2.574844
-5.097018
1.173820
-2.897275
3.124984
3.045876
3.814808
4.636782
4.713144
3.944322
2.237329
-4.042460
-0.460679
-0.350917
-0.979410
0.000032
1.084184
0.267451
1.514870
-0.352097
0.295114
0.025557
-1.011412
-1.768801
-1.488033
-0.457972
0.904655
0.127726
2.450589
-0.564125
-2.159331
2.696601
2.503594
1.695191
1.793615
0.533954
-1.705222
-2.668518
-2.901136
-2.322602
-0.893566
-1.084123
-0.267388
-1.514808
0.352162
-0.295051
-0.025494
1.011474
1.768863
1.488096
0.458035
-0.904593
-0.127662
-2.450531
0.564183
2.159391
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-3.523784
-3.968552
-5.242226
-7.536198
-7.541644
-6.769550
-6.117870
-4.242105
-2.864788
-2.897429
2.066310
1.032120
0.863502
4.245517
2.763031
0.324859
4.374756
2.757968
3.168912
4.129464
5.132614
5.471714
8.222523
7.901175
8.552516
6.837971
6.051701
7.638401
6.768864
6.001521
4.153263
4.861412
2.293569
2.338694
3.510255
3.337637
-2.066266
-1.032078
-0.863460
-4.245477
-2.762994
0.539903
-0.908584
-1.038404
-0.391369
0.459822
0.363083
-0.600679
-2.001550
-2.261517
-2.802856
-0.851742
2.024140
-2.571167
-3.771202
-5.231430
-5.370349
-1.145581
-0.576955
1.483667
1.356548
0.534160
2.097313
-0.045378
1.401596
-0.873029
-1.296477
-1.153004
-0.839799
1.481932
0.114258
1.698221
2.916412
1.324469
2.976127
2.141621
3.804479
0.851735
-2.024144
2.571162
3.771194
5.231422
-2.696539
-2.503532
-1.695130
-1.793558
-0.533898
1.705278
2.668577
2.901199
2.322665
0.893630
1.174373
-0.263419
1.129917
-1.199674
-2.577552
-2.053381
3.020035
3.483629
2.019156
3.493593
0.727997
1.489968
2.527760
1.537584
0.366461
0.661090
-1.435491
-2.194127
-2.798763
-3.653725
-3.959327
-2.870630
-2.341268
-2.969572
-0.271311
-0.855270
-1.174311
0.263484
-1.129854
1.199735
2.577614
12
H
H
H
H
H
H
H
H
H
H
H
3.4
-0.324821
-4.374712
-2.757923
-3.168868
-4.129418
-5.132572
-5.471670
-8.222479
-7.901131
-8.552474
-6.837929
5.370344
1.145573
0.576947
-1.483675
-1.356557
-0.534168
-2.097321
0.045367
-1.401605
0.873022
1.296470
2.053444
-3.019974
-3.483566
-2.019093
-3.493531
-0.727937
-1.489907
-2.527705
-1.537525
-0.366407
-0.661036
H
H
H
H
H
H
H
H
H
H
-6.051660
-7.638360
-6.768822
-6.001481
-4.153221
-4.861370
-2.293528
-2.338652
-3.510214
-3.337595
1.153003
0.839798
-1.481931
-0.114255
-1.698215
-2.916409
-1.324467
-2.976123
-2.141625
-3.804481
1.435546
2.194182
2.798823
3.653783
3.959389
2.870696
2.341328
2.969637
0.271374
0.855338
0.924687
2.415792
2.605847
2.600755
3.753965
-4.886911
2.006530
-2.803388
3.482994
3.610886
4.293370
4.827574
4.710004
4.027168
3.125499
-3.896552
0.799861
-0.607389
-1.976063
1.581544
0.159241
-0.025588
2.591933
2.634923
2.087514
0.559492
0.931884
1.141780
1.411150
0.230225
-0.014729
-0.266112
-1.409046
-2.290752
-2.024891
-0.886696
0.732762
0.804282
2.105216
-0.518387
-1.995101
2.628758
2.578165
1.651956
H•Cl− complex in chloroform (PCM) solvent environment
Optimisation parameters: Tight cut-off, ultrafine integration grid
Spin: Singlet
Energy: ‒2832.034348 a.u.
Zero-point correction: 0.879219 a.u.
Thermal correction to energy: 0.931923 a.u.
Thermal correction to enthalpy: 0.932867 a.u.
Thermal correction to Gibbs free energy: 0.784491 a.u.
Cl
O
O
N
N
C
C
C
C
C
C
C
C
O
O
O
C
C
C
C
C
C
0.075962
-4.375439
-2.248338
-2.861612
-1.866573
-1.060019
-2.449753
-3.029055
-2.222061
-0.835007
-0.246620
-3.324173
-1.480808
-6.279571
-7.225422
-5.149540
-3.416116
-3.987996
-5.246232
-7.545985
-7.616071
-7.032745
0.077401
-3.293571
4.870276
-1.612292
2.810544
-3.246713
-3.278762
-3.927004
-4.523988
-4.506470
-3.859126
-2.724040
3.942736
-0.309315
0.243012
1.179249
-1.095297
0.316574
0.418209
-0.217175
-0.766160
-0.211120
-0.012601
-1.246855
-0.859711
-1.550384
0.048859
0.030442
0.148529
1.242191
2.208156
2.073620
0.985169
-0.935411
-0.574359
-2.482701
0.453091
2.179198
-2.788267
-2.677658
-1.839447
-1.869217
-0.454270
1.771564
C
C
C
C
O
O
N
N
C
C
C
C
C
C
C
C
O
O
O
C
C
C
-6.470898
-4.643168
-3.241844
-3.204533
4.343750
1.901717
2.956191
1.780553
0.926656
2.292827
2.716969
1.779902
0.416666
-0.017069
3.299336
1.240600
6.416085
7.349051
5.316468
3.620776
4.170023
5.355067
13
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
3.5
7.684214
7.787649
7.235851
6.665984
4.792389
3.344033
3.165051
-2.035440
-1.213725
-0.604684
-4.112014
-2.676662
-0.199172
-4.194059
-2.623147
-3.230334
-4.203637
-5.070257
-5.547626
-8.217511
-7.893564
-8.647002
-6.956622
-6.333106
-7.987296
-7.096933
-6.498577
-4.628057
-5.302391
-2.589263
0.505663
0.606170
-0.573865
-1.891498
-3.285467
-3.262959
-2.751558
-1.155245
2.023931
-2.782794
-3.965768
-5.017862
-4.997074
-1.793135
-1.102013
0.991695
0.677402
0.023951
1.472407
-0.795649
0.829557
-1.091262
-1.644671
-1.061786
-0.545020
1.820003
0.657595
2.440181
3.232371
1.812725
1.564268
0.052573
-1.921082
-2.386606
-2.066019
-1.621323
-0.191033
-1.168996
0.096335
-0.838873
1.321768
3.063143
2.805638
-3.106139
-3.547342
-2.258066
-3.691936
-0.830113
-1.730157
-2.511616
-1.859340
-0.234031
-0.369203
1.787425
2.212090
2.448927
3.661447
3.737276
2.293500
2.474029
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-2.849741
-3.582015
-3.840797
2.130175
1.207070
0.590351
3.781640
2.113602
-0.320223
4.429010
2.904653
3.375679
4.467624
5.085839
5.672707
8.364703
8.005339
8.836517
7.179563
6.576276
8.223479
7.247195
6.756172
4.866786
5.383773
2.759960
2.945794
3.503494
3.762064
3.560936
1.643501
3.394548
1.493119
-1.965909
2.997172
4.408492
5.349534
5.148809
2.292431
1.658556
-0.536562
-0.124322
0.234771
-1.078771
1.232907
-0.504871
0.798342
1.450978
0.250666
-0.417574
-2.714126
-1.967152
-3.671376
-3.954480
-2.636411
-4.283154
-1.714964
-3.353329
2.459987
0.189248
0.156501
1.111088
0.103966
0.895681
-1.592268
-3.183914
-2.692166
2.814386
3.458100
2.276212
3.596242
0.619088
1.651956
2.018583
1.868126
-0.230976
-0.308945
-2.235028
-2.386835
-1.940266
-3.482965
-3.096333
-1.417624
-2.307236
-1.690855
-0.120710
0.502862
0.622490
2.741839
3.088747
-0.639342
1.706228
0.615373
H•2Cl− complex in vacuum
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒3292.055592 a.u.
Zero-point correction: 0.879274 a.u.
Thermal correction to energy: 0.934364 a.u.
Thermal correction to enthalpy: 0.935308 a.u.
Thermal correction to Gibbs free energy: 0.777840 a.u.
Cl
Cl
O
-3.593507
3.593488
-0.895339
3.241643
-3.241986
3.441119
2.412894
-2.412969
-2.358304
O
O
O
-7.224022
2.567350
5.282575
14
O
N
H
N
H
C
H
C
H
C
C
H
C
C
H
C
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
6.845160
-1.420759
-2.168397
-5.944989
-5.178294
-4.900160
-2.911659
-5.750226
-6.768366
-5.298127
-3.983368
-3.618164
-3.131525
-3.596168
-5.255959
-1.713125
-0.089547
0.020425
0.626411
0.155391
-0.714837
0.228600
1.381031
1.365081
1.374339
3.707053
3.618658
3.809516
4.962883
5.778696
4.849485
6.626251
6.905494
7.287460
6.823937
6.041863
7.800192
5.612778
4.883321
5.191916
5.873009
6.399514
4.916487
6.704065
7.031348
7.589056
-6.243017
2.117034
3.265862
3.248007
1.452751
2.078409
2.753325
3.548038
2.158510
1.878479
1.901861
2.224035
1.990259
2.836286
3.092634
2.953370
3.211994
3.521730
4.590513
3.297356
2.678909
2.777106
1.619089
3.080125
4.167445
2.566676
3.103070
2.739552
4.202567
2.500249
2.681623
1.411211
2.852801
1.798753
3.470360
3.218008
3.940329
3.698463
1.419087
2.044833
1.211892
0.124335
0.3546450
-0.343011
-0.876316
-1.690323
-0.394212
1.266697
-2.101497
-0.146785
0.555270
1.059522
1.345699
-3.447656
-3.802920
-2.517846
-2.775404
-1.221185
-0.880148
0.114505
-1.800618
-3.092226
-4.456664
-1.462432
0.358303
0.605371
-0.436154
1.607906
2.271831
1.335176
2.397164
2.599117
3.374330
2.435238
3.476047
2.474134
1.854248
2.577194
1.746275
0.241461
0.393637
0.877437
-1.225696
-1.515593
-1.358314
-2.212024
-2.751196
-1.218898
-2.954314
-3.891129
-3.221301
-2.146997
-2.807012
-1.723017
-0.240602
O
O
O
O
O
N
H
N
H
C
H
C
H
C
C
H
C
C
H
C
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
0.895691
7.223604
-2.567309
-5.282425
-6.845206
1.420958
2.168569
5.944548
5.178080
4.900659
2.912358
5.750467
6.768607
5.298103
3.983340
3.617926
3.131763
3.596665
5.256667
1.713385
0.089747
-0.020120
-0.626200
-0.155338
0.714797
-0.228473
-1.381119
-1.365322
-1.374491
-3.707151
-3.618877
-3.809724
-4.962845
-5.778751
-4.849359
-6.626050
-6.905297
-7.287349
-6.823566
-6.041184
-7.799614
-5.613015
-4.883506
-5.192022
-5.873727
-6.400464
-4.917390
-3.442009
-0.621912
-2.741971
-3.088513
-2.116378
-3.266464
-3.248556
-1.452284
-2.078255
-2.753993
-3.549158
-2.158780
-1.878656
-1.901860
-2.224151
-1.990147
-2.836814
-3.093433
-2.954245
-3.212673
-3.522368
-4.591112
-3.298221
-2.679304
-2.777362
-1.619539
-3.080285
-4.167584
-2.566723
-3.103038
-2.739462
-4.202523
-2.500108
-2.681474
-1.411072
-2.852499
-1.798471
-3.470118
-3.217518
-3.939454
-3.698359
-1.418089
-2.043449
-1.211157
-0.123118
-0.353236
0.344541
2.358093
0.638831
-1.705940
-0.614715
2.102158
0.146552
-0.555548
-1.059971
-1.346087
3.447052
3.802432
2.517256
2.774715
1.220741
0.879851
-0.114668
1.800290
3.091749
4.455944
1.462185
-0.358510
-0.605796
0.436023
-1.607917
-2.271985
-1.334948
-2.397080
-2.599163
-3.374187
-2.434815
-3.475616
-2.473769
-1.853666
-2.576510
-1.745780
-0.240663
-0.392957
-0.876480
1.226575
1.516586
1.359324
2.212682
2.752229
1.219552
2.954430
3.891162
3.221542
15
C
H
3.6
-6.704776
-7.032590
0.877008
1.691143
2.146485
2.806089
H
C
-7.589466
6.242721
0.394519
-1.266328
1.722317
0.240132
-2.963041
-2.775036
-4.054488
-2.303634
-2.665485
-1.212106
-2.245390
-1.210958
-2.907888
-2.347027
-3.170535
-2.581372
-0.776747
-1.513771
-0.770321
0.600025
0.596403
0.813965
1.716065
2.633842
1.441687
-1.763095
2.526158
1.197505
2.558768
2.602781
1.072353
2.941321
3.201163
2.005944
2.556706
2.229432
3.316279
2.080036
1.696070
2.295694
1.818427
-0.119293
0.182316
0.336611
-1.634266
-1.980173
-1.920535
-2.294170
-2.862286
-1.265411
-2.918133
-3.884230
-3.124871
-2.042026
-2.633266
-1.666328
-0.406514
2.596923
0.704881
-1.595559
-0.345838
2.260839
0.434410
-0.205849
-0.903767
-1.102021
H•2Cl− complex in chloroform (PCM) solvent environment
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒3292.224252 a.u.
Zero-point correction: 0.880498 a.u.
Thermal correction to energy: 0.935134 a.u.
Thermal correction to enthalpy: 0.936078 a.u.
Thermal correction to Gibbs free energy: 0.783296 a.u.
Cl
Cl
O
O
O
O
O
N
H
N
H
C
H
C
H
C
C
H
C
C
H
C
C
H
H
C
H
H
C
H
H
2.728562
-2.763270
-0.106828
6.673960
-3.386164
-5.975840
-7.034456
0.496136
1.257541
5.294792
4.444848
3.956237
1.855672
4.913502
5.964443
4.532098
3.181790
2.873569
2.219425
2.614000
4.258059
0.764477
-0.844442
-1.065132
-1.544324
-0.983939
-0.103233
-1.000982
-2.205299
-2.202605
-2.184699
-3.889185
3.929289
-2.534219
-1.267547
-2.448090
-2.627409
-1.150942
-2.920747
-3.170515
-2.057696
-2.585753
-2.610441
-2.959804
-2.297327
-2.213089
-2.085480
-2.170847
-1.952553
-2.506509
-2.716296
-2.778224
-2.651572
-3.092614
-4.166787
-2.681661
-2.414003
-2.655615
-1.323845
-2.866461
-3.966669
-2.448472
1.974524
-1.926530
-2.550925
-0.761449
1.606156
0.336775
-2.317131
-0.387253
0.248402
0.873033
1.090235
-3.705598
-4.087692
-2.743670
-3.006278
-1.416071
-1.071009
-0.053965
-2.025171
-3.349024
-4.736563
-1.680096
0.132560
0.231487
-0.597857
1.493316
2.103068
1.371401
2.262755
2.357321
3.282678
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
O
O
O
O
O
N
H
N
H
-4.537296
-4.497735
-4.594041
-5.783429
-6.636756
-5.722705
-7.260308
-7.482457
-8.016657
-7.339251
-6.693122
-8.370120
-5.663998
-5.074415
-5.280452
-5.548616
-6.071008
-4.492243
-6.123220
-6.223157
-7.112518
5.595206
0.064783
-6.675121
3.364224
5.993996
7.123342
-0.515019
-1.269244
-5.275610
-4.435107
16
C
H
C
H
C
C
H
C
C
H
C
C
H
H
C
H
H
C
H
H
C
3.7
-4.019074
-1.928443
-4.958173
-6.012235
-4.554174
-3.199531
-2.872218
-2.255785
-2.672538
-4.338448
-0.798644
0.835315
1.093449
1.516635
0.958337
0.098189
0.914844
2.207624
2.263268
2.169434
4.536735
2.565228
2.935550
2.245016
2.149787
2.039751
2.139809
1.926880
2.483954
2.685853
2.727446
2.648612
3.138773
4.208788
2.616512
2.633509
2.996966
1.537297
3.112486
4.214799
2.822925
3.038395
3.696810
4.112567
2.719250
2.965257
1.397346
1.073700
0.061517
2.043239
3.361483
4.723386
1.718924
-0.052052
-0.011143
0.623222
-1.486068
-2.064122
-1.503319
-2.192043
-2.153713
-3.255349
-2.207013
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
4.481673
4.646910
5.754423
6.613368
5.632886
7.281651
7.461634
8.040775
7.417588
6.793500
8.460468
5.750061
5.181138
5.340538
5.637115
6.186175
4.584757
6.173679
6.275618
7.156902
-5.596458
2.887811
4.120593
2.306200
2.629204
1.221127
2.178401
1.139406
2.819878
2.269462
3.097973
2.489939
0.709661
1.448434
0.712788
-0.669556
-0.677366
-0.872643
-1.787283
-2.710316
-1.524558
1.706717
-3.299140
-2.023769
-1.704388
-2.317578
-1.838885
0.063306
-0.250589
-0.416998
1.575056
1.948303
1.826243
2.271110
2.857744
1.252260
2.889673
3.840739
3.124457
1.992353
2.575081
1.593336
0.369493
2.280788
2.503501
-2.460214
-3.159142
1.079822
0.595600
-1.621156
-3.041403
-2.183702
3.007193
-2.043964
1.442376
-0.258625
-0.520335
-0.322404
-1.531803
-0.653262
0.324883
0.070117
-2.319642
-1.940534
-1.749884
0.103231
0.761098
H•Ca2+ complex in vacuum
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒-3048.873401 a.u.
Zero-point correction: 0.884898 a.u.
Thermal correction to energy: 0.935823 a.u.
Thermal correction to enthalpy: 0.936767 a.u.
Thermal correction to Gibbs free energy: 0.796840 a.u.
Ca
H
O
O
O
H
H
H
H
C
C
C
-0.000008
-2.854037
7.820990
-0.108249
-4.162924
3.269844
2.178860
4.438722
-3.420351
-6.520649
-7.166913
-6.690904
0.000059
3.841826
0.563383
0.493722
2.246197
3.409724
2.075959
1.089023
0.856597
2.601806
1.705306
-0.441568
0.000101
1.096631
0.897541
-2.415075
1.267834
-1.980780
-4.354838
-1.016880
-2.299310
1.697319
0.649056
-0.451276
H
C
C
C
O
N
C
C
C
N
O
C
-7.401412
2.235179
-3.458950
-3.529541
-2.164720
-6.290610
-4.502693
-4.672681
-5.704477
2.369167
-1.144967
5.609301
17
N
O
C
N
C
C
H
C
O
C
C
H
H
C
H
H
O
H
H
H
C
H
C
C
H
H
H
C
H
H
H
H
C
C
C
H
C
H
H
H
3.8
6.290440
-7.820816
6.690955
-2.369015
3.459030
4.672811
-5.305263
-5.609221
1.145001
-1.369485
-5.203985
0.354232
-6.595396
4.502753
-7.218384
-2.480852
4.162622
-6.370972
-4.924288
-4.438696
-2.235092
-2.178697
-2.493969
3.529655
0.465183
-3.321322
1.878433
1.282212
-2.160815
0.894793
6.595529
-1.387089
-1.238011
-1.014912
1.369540
5.292695
1.238159
1.561869
1.624319
-1.624105
-0.595792
-0.563424
0.441435
-3.007343
2.460105
3.041202
0.746490
-1.442529
2.044069
0.881006
3.236932
3.166061
-2.067872
1.621043
3.416747
-0.556813
-2.245982
2.048390
4.021808
-1.089133
-2.503540
-2.076176
2.472064
3.158984
2.363441
2.718121
0.312348
3.155738
2.304900
-0.021087
2.067666
-4.138270
-2.079507
-0.657135
-0.880958
-3.698214
2.079363
-0.340148
-3.086056
3.086144
-0.324721
-0.897922
0.451233
1.750028
0.322595
2.319832
0.499577
-0.760981
-0.103014
-2.959099
1.284505
-2.127896
-2.552073
-0.069967
1.923634
-1.801559
-1.268086
2.633122
2.000643
1.017029
0.520520
4.355005
-0.500643
1.532021
-4.513465
-1.177115
-2.715430
-2.704954
1.618748
-4.149838
2.552188
3.175205
3.789157
3.295046
2.959252
-0.289223
-3.789014
3.896258
0.769800
-0.769489
H
H
C
C
H
H
H
C
H
H
H
H
C
H
C
H
H
C
C
H
H
H
H
O
H
C
H
C
H
O
C
H
H
H
H
H
H
H
C
-0.354060
-0.464999
6.520271
-1.282029
-1.878419
2.480820
1.369864
2.436381
-0.894802
2.853935
3.321587
3.420395
2.494065
2.160442
2.894010
4.923875
6.370433
5.203688
7.166692
7.401317
7.217980
-3.269652
5.305064
2.164735
1.387334
-2.894191
2.713196
5.704598
-2.713065
0.108276
1.014956
8.116522
-4.755807
-1.561819
-5.292820
4.755960
-8.116796
-1.369760
-2.436361
-3.166117
-2.363559
-2.601365
-3.155856
-0.312516
0.556935
-1.956344
-0.526287
0.020958
-3.841737
-2.717849
-0.856442
-2.471902
-2.304929
-2.755180
-4.021254
-2.047510
-3.236706
-1.705347
-2.281242
-3.416190
-3.409971
-0.746592
-1.079683
4.138134
2.755288
3.807925
2.183511
-3.808079
-0.493720
0.657021
-1.306654
-3.615348
0.340189
3.697972
3.615111
1.306787
1.956390
0.526403
2.127991
4.513581
-1.698125
2.705070
2.715621
1.801726
3.175361
1.945753
4.150037
-1.096507
1.177050
2.299417
0.500742
-1.618607
-0.934141
-2.001851
-2.633644
-1.285397
-0.649536
0.257847
-1.924941
1.980910
-0.499280
0.653391
-3.175113
0.934170
1.839027
1.940671
-1.838771
2.415257
-3.294866
-1.018926
-3.238324
-3.896100
0.288098
3.238534
1.018493
-3.175224
-1.945615
H•Ca2+ complex in chloroform (PCM) solvent environment
Optimisation parameters: Tight cut-off, ultrafine integration grid
Spin: Singlet
18
Energy: ‒3049.05175263 a.u.
Zero-point correction: 0.891067 a.u.
Thermal correction to energy: 0.939995 a.u.
Thermal correction to enthalpy: 0.940939 a.u.
Thermal correction to Gibbs free energy: 0.809858 a.u.
Ca
H
O
O
O
H
H
H
H
C
C
C
H
C
C
C
O
N
C
C
C
N
O
C
N
O
C
N
C
C
H
C
O
C
C
H
H
C
H
0.024800
2.886266
-7.959324
0.169721
4.215637
-3.350633
-2.149422
-4.438233
3.477717
6.580061
7.192255
6.681850
7.406558
-2.394094
3.415313
3.442215
2.262119
6.301027
4.488119
4.567915
5.630015
-2.458088
1.115831
-5.776018
-6.265119
7.826343
-6.773613
2.365549
-3.670647
-5.065874
5.317192
5.581589
-1.337376
1.416540
5.251497
-0.423304
6.499585
-4.616643
7.287811
-0.113547
-3.644271
-0.336979
-0.772292
-2.055874
-3.549394
-2.365639
-0.930873
-1.138583
-2.371646
-1.590949
0.466476
-2.266805
-2.549526
2.412980
3.009691
-1.139473
-0.531347
1.635987
2.852328
2.053829
-3.153996
2.007777
-1.307068
0.823452
0.590807
-0.239687
3.069368
-2.444542
-3.049000
-0.675132
1.415683
-2.060464
-1.218858
-3.041443
-3.351662
1.904411
-1.505818
-3.158599
0.027422
1.512660
0.635095
-2.359999
1.501600
-1.903878
-4.243122
-0.994698
-2.279056
1.875953
0.719529
-0.535731
-0.121438
-0.449338
-0.508471
-1.771993
-0.590782
0.289000
-0.075378
-2.577266
-2.155247
-1.634691
-0.021909
0.663158
-0.338401
-0.971515
0.317175
1.549592
0.318065
2.185847
0.489346
-0.914517
0.005151
-2.887039
1.568831
-1.894794
-2.788720
-0.089252
2.161546
H
O
H
H
H
C
H
C
C
H
H
H
C
H
H
H
H
C
C
C
H
C
H
H
H
H
H
C
C
H
H
H
C
H
H
H
H
C
H
2.556225
-4.015300
6.458699
5.001035
4.457111
2.204418
2.328141
2.597827
-3.883055
-0.437876
3.451562
-1.807305
-1.321971
2.202310
-0.803920
-6.925851
1.414463
1.357465
1.146347
-1.264848
-5.054761
-1.220075
-1.372105
-1.546937
1.748442
0.363734
0.613391
-6.317925
1.315350
1.974686
-2.397829
-1.305228
-2.370267
1.108361
-2.585749
-3.275618
-3.342348
-2.422510
-1.999855
0.337659
2.314106
-1.721522
-3.760902
1.185990
2.495811
2.223760
-2.498501
-3.209540
-2.713047
-2.810094
-0.524569
-3.372659
-2.035609
-0.299051
-1.960335
4.229925
2.187823
0.753476
0.881806
3.801031
-2.365800
0.336144
2.963961
-3.156190
3.191168
2.467847
2.858529
3.228830
0.431473
-0.614847
1.956350
0.472485
0.081903
3.790519
2.660587
0.801605
2.389419
2.197987
-1.936962
-1.231454
2.751719
2.360721
0.913872
0.356834
4.168616
-0.272506
1.467306
-4.345234
-0.886369
-2.678603
-2.516127
1.787047
-4.120639
2.348886
2.969865
3.657951
3.199549
3.029323
-0.209235
-3.659818
3.976347
0.949822
-0.500483
2.008072
4.412927
-1.696311
2.541652
2.558112
1.966340
3.244899
2.078610
4.067080
-0.981761
1.257676
2.465247
0.623209
-1.475551
19
C
H
H
C
C
H
H
H
H
O
H
C
H
3.9
-2.720376
-4.618810
-6.178112
-4.971682
-7.058917
-7.298794
-6.950113
3.270971
-5.261291
-2.162158
-1.416250
2.943148
-3.139541
2.711691
4.173951
2.319234
3.378485
1.983806
2.564439
3.726650
3.476349
0.925499
0.986478
-4.381303
-2.593260
-3.935157
-0.825826
-1.893806
-2.641810
-1.222788
-0.693397
0.209489
-1.916390
1.749841
-0.442836
0.761441
-2.927371
1.198601
1.786713
C
H
O
C
H
H
H
H
H
H
H
C
-6.006891
2.599205
-0.027959
-0.954895
-8.010208
4.610491
1.587946
5.309746
-5.250067
8.145943
1.414219
2.506457
-2.102141
3.605520
0.552975
-0.929693
1.642779
3.341791
-0.781296
-3.591084
-3.660012
-1.146862
-2.311142
-0.754411
1.787726
-2.111670
2.403679
-3.234962
-1.113168
-3.546048
-3.879763
0.616531
3.064875
1.021025
-2.986863
-1.946084
-3.495759
-4.311594
-3.635355
-1.428280
-1.428361
-2.236758
2.236784
-3.402941
-3.402756
-2.169925
-2.428034
-2.169880
-1.694075
-1.484658
-1.694136
-2.313899
-2.313902
-3.635787
-4.311786
-3.495710
-0.491433
0.603935
1.280571
-0.446148
-0.446180
-0.023090
0.023470
0.411633
0.412062
-1.046975
-0.395696
-1.047007
-2.361873
-3.025121
-2.361843
-0.339872
-0.339740
1.279675
0.602353
-0.493185
H•2Ca2+ complex in vacuum
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒3725.691980 a.u.
Zero-point correction: 0.888628 a.u.
Thermal correction to energy: 0.940704 a.u.
Thermal correction to enthalpy: 0.941648 a.u.
Thermal correction to Gibbs free energy: 0.798997 a.u.
Ca
Ca
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
O
-5.187013
5.187069
-3.396284
3.395960
-6.230450
-6.230316
-2.702358
2.702533
1.211955
-0.000053
-1.212160
-1.205441
-0.000239
1.205057
-2.520458
2.520336
-3.854744
-5.044686
-5.708966
-7.612401
-0.000013
0.000071
1.428472
1.428181
2.236668
-2.236680
3.402658
3.402948
2.169906
2.428096
2.169976
1.694182
1.484685
1.694093
2.313927
2.313871
3.635180
4.311486
3.495792
-0.000030
-0.000007
0.000109
0.446414
0.446340
0.021416
-0.021271
-0.412196
-0.411336
1.047210
0.395846
1.047061
2.361931
3.025263
2.362070
0.339804
0.340092
-1.280672
-0.604075
0.491382
-0.000289
C
C
C
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
-5.708907
-5.044658
-3.854695
3.396117
-3.396136
6.230348
6.230455
2.702527
-2.702337
-1.212060
0.000018
1.212061
1.205222
-0.000040
-1.205278
2.520426
-2.520374
3.855172
5.044883
5.708554
20
O
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
7.612335
5.708593
5.044902
3.855175
-2.006753
2.007029
0.000036
-2.146545
-0.000311
2.146084
-4.145536
-3.506129
-4.731910
-5.774455
-5.001286
-6.527072
-5.001200
-6.527031
-5.774431
-4.731920
-4.145471
-3.506044
2.006996
-2.006750
0.000045
2.146275
-0.000060
-2.146353
4.146080
3.506844
4.731992
5.775032
-0.000033
3.495745
4.311756
3.635735
4.135273
4.135646
2.747002
1.503432
1.151329
1.503259
2.670560
4.256008
5.268839
4.562431
3.243249
4.063192
-3.243146
-4.063057
-4.562561
-5.268926
-2.670777
-4.256268
-4.135610
-4.135382
-2.746934
-1.503279
-1.151326
-1.503390
-2.671331
-4.256963
-5.269037
-4.562903
-0.000567
0.493459
-0.602124
-1.279400
-0.352811
-0.351718
-0.645191
2.869752
4.058984
2.870007
-1.708914
-2.110733
-0.168025
-1.384569
1.284630
0.948807
-1.284640
-0.948953
1.384419
0.167809
1.708901
2.110552
0.352018
0.352568
0.645344
-2.869773
-4.058850
-2.869719
1.708202
2.109596
0.166158
1.382433
H
H
H
H
H
H
H
H
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
5.000420
6.526384
5.000459
6.526394
5.775043
4.732024
4.146059
3.506847
8.388326
7.520494
-7.520514
-8.388369
-8.388321
-7.520504
8.388282
7.520677
8.691888
9.284279
7.988654
7.393707
-7.988569
-7.393713
-9.284435
-8.691744
-9.284474
-8.691553
-7.393902
-7.988470
8.691260
9.284586
7.394357
7.988681
-3.242861
-4.062954
3.242897
4.063041
4.562835
5.269035
2.671257
4.256877
1.207773
2.292410
2.291718
1.207776
-1.207874
-2.291666
-1.207879
-2.292201
1.443567
1.073829
3.269572
2.147381
3.269115
2.145427
1.073233
1.444640
-1.073250
-1.444932
-2.145140
-3.269126
-1.444082
-1.073727
-2.146633
-3.269483
-1.285929
-0.951298
1.286208
0.951561
-1.382226
-0.165983
-1.707886
-2.109346
-0.015523
-0.608278
-0.610335
-0.016355
0.015891
0.610228
0.014441
0.608087
1.011261
-0.632787
-0.448806
-1.688519
-0.452019
-1.690402
-0.633325
1.010240
0.632717
-1.010699
1.690285
0.452051
-1.012421
0.631147
1.688310
0.448908
-0.000719
0.001712
3.10 H•2Ca2+ complex in chloroform (PCM) solvent environment
Optimisation parameters: Tight cut-off, ultrafine integration grid
Spin: Singlet
Energy: ‒3726.232317 a.u.
Zero-point correction: 0.894326 a.u.
Thermal correction to energy: 0.944277 a.u.
Thermal correction to enthalpy: 0.945222 a.u.
Thermal correction to Gibbs free energy: 0.813380 a.u.
Ca
5.133634
-0.000715
0.001699
Ca
-5.133632
21
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
H
H
H
H
H
3.373352
-3.373355
6.230442
6.232574
2.743611
-2.743615
-1.208302
-0.000002
1.208297
1.203489
-0.000004
-1.203496
2.521677
-2.521682
3.951171
5.109400
5.660653
7.583887
5.662980
5.108243
3.948470
-3.374236
3.374240
-6.232575
-6.230442
-2.742151
2.742154
1.208349
0.000002
-1.208344
-1.203530
0.000003
1.203536
-2.521542
2.521545
-3.948469
-5.108242
-5.662978
-7.583886
-5.660655
-5.109404
-3.951172
2.057007
-2.057013
-0.000002
2.147111
-0.000004
1.502835
1.502833
2.264889
-2.264737
3.498211
3.498211
2.267019
2.552597
2.267019
1.742016
1.508304
1.742017
2.405276
2.405276
3.707571
4.338414
3.524384
0.000412
-3.524039
-4.338225
-3.707680
-1.504058
-1.504054
-2.264738
2.264889
-3.498347
-3.498343
-2.266376
-2.552287
-2.266379
-1.740398
-1.506136
-1.740396
-2.405563
-2.405559
-3.707682
-4.338225
-3.524040
0.000414
3.524386
4.338414
3.707571
4.240972
4.240973
2.916988
1.521041
1.125254
-0.314117
-0.314112
-0.230373
0.229565
0.530668
0.530670
-0.895487
-0.253287
-0.895487
-2.191097
-2.847607
-2.191097
-0.202174
-0.202171
1.321090
0.549425
-0.611163
-0.013228
0.611594
-0.547275
-1.316840
0.320876
0.320872
0.229574
-0.230366
-0.524533
-0.524538
0.902377
0.260404
0.902379
2.197590
2.853867
2.197588
0.208921
0.208918
-1.316834
-0.547268
0.611601
-0.013262
-0.611154
0.549436
1.321097
0.505406
0.505405
0.771255
-2.681005
-3.863587
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
-2.147118
4.243972
3.675924
4.791242
5.910065
4.877160
6.428873
4.881592
6.432389
5.906955
4.790519
4.240109
3.671869
-2.054987
2.054990
0.000002
-2.147152
0.000003
2.147158
-4.240106
-3.671870
-4.790517
-5.906954
-4.881590
-6.432386
-4.877162
-6.428877
-5.910069
-4.791248
-4.243973
-3.675923
-8.358776
-7.501548
7.501545
8.358775
8.358926
7.499158
-8.358923
-7.499155
-8.679231
-9.244878
-7.998285
-7.360255
7.998285
7.360247
9.244876
8.679232
1.521042
2.744729
4.359449
5.308217
4.557139
3.281363
4.104993
-3.280553
-4.105068
-4.558242
-5.307514
-2.744946
-4.359880
-4.240595
-4.240592
-2.917311
-1.519204
-1.122296
-1.519200
-2.744948
-4.359883
-5.307515
-4.558244
-3.280553
-4.105069
3.281368
4.104995
4.557133
5.308219
2.744728
4.359447
1.198915
2.340486
2.340491
1.198914
-1.197519
-2.342191
-1.197518
-2.342195
1.357519
1.108177
3.289680
2.280587
3.289681
2.280604
1.108187
1.357505
-2.681003
1.749444
2.154341
0.145817
1.267492
-1.332452
-1.136901
1.334978
1.135125
-1.267074
-0.142090
-1.746254
-2.149383
-0.499239
-0.499241
-0.763909
2.687401
3.869548
2.687397
-1.746246
-2.149377
-0.142081
-1.267066
1.334984
1.135133
-1.332444
-1.136891
1.267504
0.145831
1.749451
2.154348
-0.076175
0.417035
0.417035
-0.076158
0.054307
-0.426423
0.054289
-0.426423
-1.112919
0.563274
0.186256
1.504108
0.186247
1.504108
0.563294
-1.112903
22
H
H
H
H
9.241762
8.684624
7.350481
7.998594
-1.111518
-1.349246
-2.288343
-3.289527
-0.590294
1.090496
-1.512786
-0.193701
H
H
H
H
-8.684625
-9.241758
-7.350471
-7.998595
-1.349230
-1.111527
-2.288359
-3.289527
1.090480
-0.590316
-1.512785
-0.193692
-2.770222
-2.770262
-1.498883
-1.734516
-1.498957
-0.970499
-0.710459
-0.970413
-1.785200
-1.785120
-3.036771
-3.960178
-3.417157
0.000228
3.417260
3.960060
3.036364
1.210228
2.344910
2.344533
1.209616
-1.210124
-2.345025
-1.209560
-2.344459
3.332824
3.332325
2.095988
0.775581
-0.008586
-0.008743
1.600232
0.953088
1.600398
2.894315
3.535423
2.894144
0.882190
0.881902
-0.981794
-0.512870
0.601918
-0.000218
-0.601563
0.513450
0.982542
-0.085391
0.389057
0.389056
-0.084797
0.085150
-0.388659
0.084138
-0.389650
0.157109
0.157774
0.069807
-3.398032
3.11 2Ca2+•H•2Cl− complex in vacuum
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒4646.552229 a.u.
Zero-point correction: 0.888590 a.u.
Thermal correction to energy: 0.943903 a.u.
Thermal correction to enthalpy: 0.944847 a.u.
Thermal correction to Gibbs free energy: 0.794324 a.u.
Ca
Ca
Cl
Cl
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
O
O
O
O
5.178254
-5.178336
0.000074
-0.000089
3.513740
-3.513446
6.195968
6.195719
2.459133
-2.458674
-1.210649
0.000172
1.210871
1.209697
-0.000050
-1.209690
2.480143
-2.479809
3.501920
4.625697
5.499945
7.593493
5.499464
4.625437
3.501699
-3.513699
3.513443
-6.196255
-6.195555
-0.000160
0.000004
4.387876
-4.386959
1.096866
1.096516
2.202509
-2.202901
2.770118
2.769483
1.498563
1.733686
1.498784
0.971256
0.711560
0.971053
1.785004
1.784571
3.037114
3.960408
3.416993
-0.000205
-3.417362
-3.960501
-3.037078
-1.096995
-1.096898
-2.202586
2.202830
-0.000038
0.000439
0.985385
-0.986708
-1.108738
-1.108224
-0.240847
0.241237
0.008638
0.009438
-1.599976
-0.952694
-1.600272
-2.894566
-3.535773
-2.894274
-0.882021
-0.881453
0.981609
0.512185
-0.602503
-0.000104
0.602500
-0.512497
-0.981787
1.108952
1.108505
0.240596
-0.240416
N
N
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
-2.459268
2.458929
1.210657
-0.000139
-1.210861
-1.209721
0.000006
1.209661
-2.480158
2.479881
-3.501955
-4.625851
-5.500213
-7.593606
-5.499173
-4.624960
-3.501359
-8.352944
-7.467406
7.467610
8.353180
8.352949
7.467353
-8.353373
-7.467744
1.591150
-1.590759
0.000274
2.152312
23
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-0.000136
-2.152393
3.899859
2.995669
4.182623
5.241597
4.903442
6.246023
4.902744
6.245380
5.241483
4.182342
3.899654
2.995439
-1.591255
1.590941
-0.000200
-2.152356
0.000068
2.152349
-3.899758
-2.995618
-4.182886
-5.241670
0.310653
0.775203
2.082243
3.506196
4.900235
4.220571
3.152315
4.159018
-3.152739
-4.159506
-4.220367
-4.900449
-2.082143
-3.505963
-3.332772
-3.332854
-2.097973
-0.774344
-0.308861
-0.774178
-2.081733
-3.505562
-4.900184
-4.219942
-4.545097
-3.397506
1.356527
1.831232
0.159380
1.383580
-1.477892
-0.908797
1.477757
0.908910
-1.383877
-0.160055
-1.356497
-1.831512
-0.157388
-0.157404
-0.069043
3.397557
4.544472
3.397253
-1.356406
-1.831528
-0.160409
-1.384444
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-4.903802
-6.246282
-4.902586
-6.245008
-5.240905
-4.181690
-3.899445
-2.994989
-8.665754
-9.242847
-7.928257
-7.349103
7.928696
7.348899
9.242629
8.666739
9.242624
8.666131
7.348671
7.928417
-8.667187
-9.242668
-7.348760
-7.928941
-3.152732
-4.159314
3.152719
4.159574
4.219909
4.899974
2.081449
3.505067
1.355777
1.144910
3.302240
2.318516
3.301736
2.318431
1.144071
1.355036
-1.144916
-1.355356
-2.318989
-3.302216
-1.355104
-1.143902
-2.318201
-3.301679
1.477450
0.907916
-1.476936
-0.907750
1.384908
0.161131
1.357165
1.832302
-1.126538
0.552424
0.118759
1.481051
0.118702
1.481012
0.553625
-1.125733
-0.552994
1.126229
-1.480621
-0.118219
1.124981
-0.554487
-1.481573
-0.119543
3.12 2Ca2+•H•2Cl− complex in chloroform (PCM) solvent environment
Optimisation parameters: Default cut-off, fine integration grid
Spin: Singlet
Energy: ‒4646.759495 a.u.
Zero-point correction: 0.892216 a.u.
Thermal correction to energy: 0.947078 a.u.
Thermal correction to enthalpy: 0.948022 a.u.
Thermal correction to Gibbs free energy: 0.801552 a.u.
Ca
Ca
Cl
Cl
O
O
O
O
N
5.152056
-5.151520
-0.002118
0.001707
3.443894
-3.441733
6.231657
6.214896
2.590234
0.004510
0.004593
-5.184141
5.264610
-1.395990
-1.396462
-2.245019
2.250594
-3.252101
0.061378
0.080782
-0.915976
0.637818
0.741176
0.755351
0.291387
-0.198780
-0.234341
N
C
C
C
C
C
C
C
C
-2.591334
-1.205251
0.000945
1.209857
1.211571
0.006410
-1.201518
2.497368
-2.495660
-3.252452
-1.973323
-2.245798
-1.973330
-1.420482
-1.159739
-1.420397
-2.198586
-2.198877
-0.223269
1.288398
0.646493
1.283218
2.566682
3.213513
2.571816
0.574095
0.584687
24
C
C
C
O
C
C
C
O
O
O
O
N
N
C
C
C
C
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
3.722831
4.913489
5.618965
7.592439
5.636806
4.885035
3.684594
-3.451983
3.449593
-6.210948
-6.234000
-2.573600
2.573556
1.206891
-0.001143
-1.211448
-1.211937
-0.005718
1.202807
-2.497323
2.495161
-3.683416
-4.883807
-5.635178
-7.592074
-5.621499
-4.915356
-3.727143
-8.362729
-7.497900
7.508976
8.363395
8.354308
7.464452
-8.354462
-7.473138
1.789175
-1.790438
-0.001208
2.156836
0.008556
-2.144683
4.032717
3.345225
-3.483442
-4.206843
-3.493572
0.017630
3.468134
4.276404
3.591757
1.366116
1.365810
2.252650
-2.243296
3.286273
3.284365
1.885594
2.199977
1.885488
1.243621
0.937400
1.243756
2.171264
2.170723
3.596771
4.280520
3.469219
0.016780
-3.490775
-4.207639
-3.484398
-1.183070
-2.329384
-2.325775
-1.182228
1.223697
2.364220
1.222946
2.360037
-3.894057
-3.894200
-2.640550
-1.201598
-0.745307
-1.201426
-2.525138
-4.090828
-1.119240
-0.488556
0.653993
0.095626
-0.697321
0.347492
1.000025
-0.703043
-0.716283
-0.185235
0.305223
0.118237
0.111249
-1.302905
-0.682766
-1.298342
-2.539772
-3.164956
-2.544334
-0.604924
-0.613772
1.007503
0.353931
-0.688753
0.059199
0.671711
-0.468307
-1.103784
0.128695
-0.348874
-0.336921
0.166609
0.033774
0.478886
-0.002221
0.469266
-0.324519
-0.316522
-0.363704
3.054949
4.217477
3.064101
-1.550245
-1.946113
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
4.575270
5.630517
4.916996
6.395222
4.969864
6.438890
5.571396
4.550288
3.993835
3.281528
-1.766187
1.766525
0.000642
-2.156027
-0.007542
2.145155
-3.993559
-3.279097
-4.549179
-5.570368
-4.968166
-6.438084
-4.920090
-6.398144
-5.632768
-4.574698
-4.038506
-3.352411
-8.687754
-9.246205
-7.994395
-7.355410
8.001136
7.388509
9.257674
8.671068
9.222767
8.702403
7.296234
7.951519
-8.686366
-9.233231
-7.324658
-7.955844
-5.176581
-4.429941
-3.248395
-4.144468
3.159940
4.075119
4.579921
5.202163
2.670648
4.253678
3.926260
3.924721
2.665196
0.991901
0.452515
0.992086
2.677229
4.260196
5.205328
4.584985
3.159910
4.073967
-3.242423
-4.140151
-4.436166
-5.174956
-2.526301
-4.092425
-1.334094
-1.102150
-3.277005
-2.281236
-3.274773
-2.269850
-1.093842
-1.342232
1.156471
1.368150
2.325811
3.316737
1.377160
1.147662
2.311101
3.314891
-0.101520
-1.289737
1.452871
1.074408
-1.504638
-1.134442
1.149042
-0.137513
1.504487
1.771204
0.147852
0.143761
0.296787
-3.014436
-4.136937
-3.022461
1.514239
1.776721
-0.132963
1.154928
-1.495637
-1.127310
1.470039
1.094164
-1.267550
-0.077453
-1.534448
-1.931492
1.165514
-0.516137
-0.109156
-1.436407
-0.093761
-1.426684
-0.462129
1.207301
0.700243
-0.996476
1.563116
0.240867
-1.036349
0.649750
1.555959
0.232108
25
4.
Infrared spectra from vibrational frequency calculations (PBE1PBE/6-31+G(d))
The predicted effect of binding is reflected in the position of the N-H stretching frequencies. No
scaling factor has been applied to the frequencies.
Figure S1. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of free host (H) in vacuum
Figure S2. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of free host (H) in
chloroform (PCM) solvent environment
26
27
Figure S3. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•Cl− complex in
vacuum
Figure S4. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•Cl− complex in
chloroform (PCM) solvent environment
28
Figure S5. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•2Cl− complex in
vacuum
Figure S6. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•2Cl− complex in
chloroform (PCM) solvent environment
29
Figure S7. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•Ca2+ complex in
vacuum
Figure S8. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•Ca2+ complex in
chloroform (PCM) solvent environment
30
Figure S9. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•2Ca2+ complex in
vacuum
Figure S10. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of H•2Ca2+ complex in
chloroform (PCM) solvent environment
31
Figure S11. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of 2Ca2+•H•2Cl− complex
in vacuum
Figure S12. DFT (PBE1PBE/6-31+G(d)) computed infrared spectrum of 2Ca2+•H•2Cl− complex
in chloroform (PCM) solvent environment
32
5.
5.1
Summary of computed energies for ∆E calculations
Energy calculation summary (with BSSE counterpoise correction) in vacuum using DFT at
PBE1PBE/6-311++G(d,p)//PBE1PBE/6-31+G(d)
[H•G + G] in stepwise
energy (a.u.)
‒2832.55685721
Cl•H•Cl complex
‒3292.67133212
H•Cl complex (CP)
‒2832.55391256
Cl•H•Cl complex (CP)
‒3292.66750920
HostH•Cl
‒2372.32817820
HostCl•H•Cl
‒2832.52429841
ClH•Cl
‒460.12934198
ClCl•H•Cl
‒460.12934161
H•2Cl complex
‒3292.67133212
H•2Cl complex (CP)
‒3292.66750920
HostH•2Cl
‒2372.32604410
2ClH•2Cl
‒920.25868323
H•Ca complex
‒3049.48509172
Ca•H•Ca complex
‒3726.35605113
H•Ca complex (CP)
‒3049.48239656
Ca•H•Ca complex (CP)
‒3726.35193550
HostH•Ca
‒2372.29377742
HostCa•H•Ca
‒3049.41063766
CaH•Ca
‒676.71684190
CaCa•H•Ca
‒676.71684190
H•2Ca complex
‒3726.35605113
H•2Ca complex (CP)
‒3726.35193550
HostH•2Ca
‒2372.23384286
2CaH•2Ca
‒1353.43368380
2Ca•H•2C1 complex
‒4647.28212153
2Ca•H•2C1 complex (CP)
‒4647.27336880
Host2Ca•H•2Cl
‒3726.32833854
2Cl2Ca•H•2Cl
‒920.25868395
2Cl•H•2Ca complex
‒4647.28212153
2Cl•H•2Ca complex (CP)
‒4647.27336880
Host2Cl•H•2Ca
‒3292.54034207
2Ca2Cl•H•2Ca
‒1353.43368380
H•2Ca•2Cl complex
‒4647.28212153
H•2Ca•2Cl complex (CP)
‒4647.27336880
HostH•2Ca•2Cl
‒2372.23149940
2Ca•2ClH•2Ca•2Cl
‒2273.69236776
species
energy (a.u.)
free host (H)
‒2372.36753498
H•Cl complex
33
5.2
Energy calculation summary (with BSSE counterpoise correction) in chloroform (PCM)
solvent environment using DFT at PBE1PBE/6-311++G(d,p)//PBE1PBE/6-31+G(d)
species
energy (a.u.)
[H•G + G] in stepwise
energy (a.u.)
free host (H)
‒2372.39100780
H•Cl complex
‒2832.62041511
Cl•H•Cl complex
‒3292.83919741
H•Cl complex (CP)
‒2832.61747045
Cl•H•Cl complex (CP)
‒3292.83537448
HostH•Cl
‒2372.36324990
HostCl•H•Cl
‒2832.60797914
ClH•Cl
‒460.21835032
ClCl•H•Cl
‒460.21834996
H•2Cl complex
‒3292.83919741
H•2Cl complex (CP)
‒3292.83537448
HostH•2Cl
‒2372.36697538
2ClH•2Cl
‒920.43670064
H•Ca complex
‒3049.66023823
Ca•H•Ca complex
‒3726.88949508
H•Ca complex (CP)
‒3049.65754307
Ca•H•Ca complex (CP)
‒3726.88537946
HostH•Ca
‒2372.33140403
HostCa•H•Ca
‒3049.61234701
CaH•Ca
‒677.16305925
CaCa•H•Ca
‒677.16305925
H•2Ca complex
‒3726.88949508
H•2Ca complex (CP)
‒3726.88537946
HostH•2Ca
‒2372.29031702
2CaH•2Ca
‒1354.32611850
2Ca•H•2C1 complex
‒4647.47763797
2Ca•H•2C1 complex (CP)
‒4647.46888524
Host2Ca•H•2Cl
‒3726.88213182
2Cl2Ca•H•2Cl
‒920.43670064
2Cl•H•2Ca complex
‒4647.47763797
2Cl•H•2Ca complex (CP)
‒4647.46888524
Host2Cl•H•2Ca
‒3292.74780170
2Ca2Cl•H•2Ca
‒1354.32611850
H•2Ca•2Cl complex
‒4647.47763797
H•2Ca•2Cl complex (CP)
‒4647.46888524
HostH•2Ca•2Cl
‒2372.28524612
2Ca•2ClH•2Ca•2Cl
‒2274.76281914
34
5.3
5.4
Energy calculation summary (with BSSE counterpoise correction) in vacuum and
chloroform (SMD) solvent environment using DFT at PBE1PBE/6-311++G(2df,2p)
//PBE1PBE/6-31+G(d)
species in vacuum
energy (a.u.)
species in CHCl3 (SMD)
energy (a.u.)
free host (H)
‒2372.49830585
free host (H)
‒2372.55440258
H•Cl complex
‒2832.68870830
H•Cl complex
‒2832.78056042
H•Cl complex (CP)
‒2832.68577224
H•Cl complex (CP)
‒2832.77762436
HostH•Cl
‒2372.45970537
HostH•Cl
‒2372.53110379
ClH•Cl
‒460.12934198
ClH•Cl
‒460.21566285
H•Ca complex
‒3049.61111553
H•Ca complex
‒3049.83580133
H•Ca complex (CP)
‒3049.60935652
H•Ca complex (CP)
‒3049.83404232
HostH•Ca
‒2372.42562013
HostH•Ca
‒2372.49455835
CaH•Ca
‒676.71684190
CaH•Ca
‒677.20746852
Energy calculation summary (with BSSE counterpoise correction) in vacuum and
chloroform (SMD) solvent environment using DFT at B3LYP/6-311++G(2df,2p)
//PBE1PBE/6-31+G(d)
species in vacuum
energy (a.u.)
species in CHCl3 (SMD)
energy (a.u.)
free host (H)
‒2375.23915210
free host (H)
‒2375.29711322
H•Cl complex
‒2835.60096817
H•Cl complex
‒2835.69506615
H•Cl complex (CP)
‒2835.59803211
H•Cl complex (CP)
‒2835.69213009
HostH•Cl
‒2375.20417439
HostH•Cl
‒2375.27747805
ClH•Cl
‒460.30372729
ClH•Cl
‒460.38969907
H•Ca complex
‒3052.54297078
H•Ca complex
‒3052.76856380
H•Ca complex (CP)
‒3052.54121177
H•Ca complex (CP)
‒3052.76680479
HostH•Ca
‒2375.17032710
HostH•Ca
‒2375.23807207
CaH•Ca
‒676.90578468
CaH•Ca
‒677.39647677
35
5.5
5.6
Energy calculation summary (with BSSE counterpoise correction) in vacuum and
chloroform (SMD) solvent environment using DFT at M06/6-311++G(2df,2p)
//PBE1PBE/6-31+G(d)
species in vacuum
energy (a.u.)
species in CHCl3 (SMD)
energy (a.u.)
free host (H)
‒2373.67263301
free host (H)
‒2373.72084823
H•Cl complex
‒2833.99404700
H•Cl complex
‒2834.07899725
H•Cl complex (CP)
‒2833.99111094
H•Cl complex (CP)
‒2834.07606119
HostH•Cl
‒2373.62291623
HostH•Cl
‒2373.68853424
ClH•Cl
‒460.26179913
ClH•Cl
‒460.34813634
H•Ca complex
‒3050.94746647
H•Ca complex
‒3051.17078252
H•Ca complex (CP)
‒3050.94570746
H•Ca complex (CP)
‒3051.16902351
HostH•Ca
‒2373.59655232
HostH•Ca
‒2373.66498003
CaH•Ca
‒676.88188048
CaH•Ca
‒677.37267236
Energy calculation summary (with BSSE counterpoise correction) in vacuum and
chloroform (SMD) solvent environment using DFT at B3LYP-GD3BJ/6-311++G(2df,2p)
//PBE1PBE/6-31+G(d)
species in vacuum
energy (a.u.)
species in CHCl3 (SMD)
energy (a.u.)
free host (H)
‒2375.46250009
free host (H)
‒2375.51363224
H•Cl complex
‒2835.82169109
H•Cl complex
‒2835.90828777
H•Cl complex (CP)
‒2835.81875503
H•Cl complex (CP)
‒2835.90535171
HostH•Cl
‒2375.41141243
HostH•Cl
‒2375.47895625
ClH•Cl
‒460.30372729
ClH•Cl
‒460.38969907
H•Ca complex
‒3052.79094487
H•Ca complex
‒3053.01637019
H•Ca complex (CP)
‒3052.78918586
H•Ca complex (CP)
‒3053.01461118
HostH•Ca
‒2375.39047133
HostH•Ca
‒2375.45812094
CaH•Ca
‒676.90578468
CaH•Ca
‒677.39647677
36
5.7
6.
Energy calculation summary (with BSSE counterpoise correction) in vacuum and
chloroform (SMD) solvent environment using DFT at ωB97X-D/6-311++G(2df,2p)
//PBE1PBE/6-31+G(d)
species in vacuum
energy (a.u.)
species in CHCl3 (SMD)
energy (a.u.)
free host (H)
‒2374.50223334
free host (H)
‒2374.55354043
H•Cl complex
‒2834.83840009
H•Cl complex
‒2834.92677280
H•Cl complex (CP)
‒2834.83546403
H•Cl complex (CP)
‒2834.92383674
HostH•Cl
‒2374.45184316
HostH•Cl
‒2374.51992872
ClH•Cl
‒460.28225673
ClH•Cl
‒460.36858799
H•Ca complex
‒3051.81248118
H•Ca complex
‒3052.03762802
H•Ca complex (CP)
‒3051.81072217
H•Ca complex (CP)
‒3052.03586901
HostH•Ca
‒2374.42763645
HostH•Ca
‒2374.49761791
CaH•Ca
‒676.90923384
CaH•Ca
‒677.39966821
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