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ELECTRONIC SUPPLEMENTARY INFORMATION
Complexes Containing CO2 and SO2.
Mixed Dimers, Trimers and Tetramers
†, ‡
Luis Miguel Azofra
‡,
and Steve Scheiner *
†
Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006, Madrid, Spain
‡
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-
0300, USA
*Author to whom correspondence should be addressed.
Fax: (+1) 435-797-3390
E-mail: [email protected]
Page
Figure S1. MEP on the vdW surface for the monomers
S2
Table S1. NBO analysis for the (CO2)2:SO2 heterotrimers
S2
Figure S2. (SO2)2 homodimers
S2
Table S2. Interaction energy for the (SO2)2 homodimers
S3
Table S3. NBO analysis for the CO2:(SO2)2 heterotrimers
S3
Figure S3. (CO2)3:SO2 minima
S4
Table S4. Multi-body analysis of the (CO2)3:SO2 heterotetramers
S4
Figure S4. CO2:(SO2)3 minima
S5
Table S5. Multi-body analysis of the CO2:(SO2)3 heterotetramers
S6
S1
Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics
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Figure S1. Molecular Electrostatic Potential (MEP) on the van der Walls (vdW)
isodensity surface (±0.001 au). Black points are maxima and green points are minima in
the electrostatic surface. Blue, green, yellow and red regions go from more negative to
more positive values, in that order.
CO2
SO2
Table S1. Second-order perturbation NBO energy, E(2) in kcal/mol, for the (CO2)2:SO2
heterotrimers at B97XD/aug-cc-pVDZ computational level, applying an E(2)
threshold of 0.5 kcal/mol.
Complex Donor/Acceptor
CO2(1)/CO2(2)
SO2/CO2(1)
B1
SO2/CO2(1)
CO2(2)/SO2
CO2(1)/CO2(2)
SO2/CO2(1)
B2
SO2/CO2(1)
CO2(2)/SO2
SO2/CO2(1)
SO2/CO2(1)
B3
SO2/CO2(2)
SO2/CO2(1)
B4
SO2/CO2(2)
Type
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(SO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(SO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(CO)
Olpπ*(CO)
E(2)
0.93
0.75
0.75
0.81
1.24
0.88
0.80
0.78
0.91
0.79
1.43
1.36
1.36
Figure S2. (SO2)2 homodimers at MP2/aug-cc-pVDZ computational level. Blue dot
lines link atoms which present interatomic AIM BCPs, with distances in Å. Complexes
are arranged in ascending order of energy.
F1 (C1)
F2 (Ci)
S2
F3 (C2)
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Table S2. Interaction energy in kcal/mol at MP2/aug-cc-pVDZ and at CCSD(T)/aug-ccpVTZ (single point) computational levels for the (SO2)2 homodimers.
Complex
F1
F2
F3
a
MP2
Eint
Eint + CCa
–3.76
–2.39
–3.39
–2.23
–3.21
–1.88
CCSD(T)
Eint
Eint + CCa
–3.65
–3.02
–3.23
–2.66
–3.09
–2.52
Counterpoise correction of the Basis Set Superposition Error (BSSE).
Table S3. Second-order perturbation NBO energy, E(2) in kcal/mol, for the CO2:(SO2)2
heterotrimers at B97XD/aug-cc-pVDZ computational level, applying an E(2)
threshold of 0.5 kcal/mol.
Complex Donor/Acceptor
Type
SO2(1)/CO2
Olpπ*(CO)
SO2(1)/CO2
Olpπ*(CO)
C1
SO2(2)/SO2(1)
Olpπ*(SO)
SO2(2)/SO2(1) π(SO)π*(SO)
SO2(1)/CO2
Olpπ*(CO)
SO2(1)/CO2
C2
Olpπ*(CO)
SO2(2)/SO2(1)
Olpπ*(SO)
SO2(1)/CO2
Olpπ*(CO)
C3
SO2(2)/CO2
Olpπ*(CO)
CO2/SO2(1)
Olpπ*(SO)
SO2(1)/SO2(2) π(SO)π*(SO)
C4
SO2(2)/CO2
Olpπ*(CO)
SO2(1)/CO2
Olpπ*(CO)
SO2(2)/CO2
C5
Olpπ*(CO)
SO2(2)/SO2(1)
Olpσ*(SO)
CO2/SO2(2)
Olpπ*(SO)
SO
(1)/CO
C6
OlpClv
2
2
SO2(2)/SO2(1)
Olpπ*(SO)
SO2(1)/SO2(2)
Olpπ*(SO)
C7
SO2(2)/CO2
Olpπ*(CO)
CO2/SO2(2)
Olpπ*(SO)
C8
SO2(2)/CO2
Olpπ*(CO)
SO2(1)/CO2
C9
Olpπ*(CO)
SO2(1)/CO2
Olpπ*(CO)
C10
SO2(2)/CO2
Olpπ*(CO)
SO2(1)/CO2
Olpπ*(CO)
C11
SO2(2)/CO2
Olpπ*(CO)
S3
E(2)
1.11
0.81
1.37
0.51
0.88
0.98
0.61
1.22
1.29
1.88
1.16
0.91
1.44
1.09
0.70
0.91
2.02
1.88
0.66
1.47
0.85
0.84
1.39
1.33
1.44
1.45
1.45
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Figure S3. Most stable (CO2)3:SO2 minima (less than 1 kcal/mol) at MP2/aug-cc-pVDZ
computational level. Blue dot lines link atoms which present interatomic AIM BCPs.
Complexes are arranged in ascending order of energy.
D1 (C1)
D2 (C1)
D3 (C1)
Table S4. Multi-body analysis in kcal/mol for the (CO2)3:SO2 complexes at MP2/augcc-pVDZ computational level.
Complex
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
D13
D14
D15
D16
2E
–11.36
–10.84
–10.89
–10.47
–10.40
–10.45
–10.44
–10.43
–10.39
–10.33
–10.33
–9.93
–9.39
–9.25
–8.16
–6.99
3E
–0.59
–0.56
–0.43
–0.42
–0.44
–0.36
–0.35
–0.38
–0.37
–0.36
–0.31
–0.44
–0.22
–0.25
0.08
–0.01
S4
4E
0.00
0.00
0.01
0.02
0.03
0.04
0.02
0.04
0.02
0.02
0.06
0.06
–0.01
0.00
–0.04
0.02
total Eint
–11.95
–11.40
–11.31
–10.87
–10.81
–10.77
–10.77
–10.77
–10.74
–10.67
–10.58
–10.31
–9.62
–9.50
–8.12
–6.98
Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics
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Figure S4. Most stable CO2:(SO2)3 minima (less than 1 kcal/mol) at MP2/aug-cc-pVDZ
computational level. Blue dot lines link atoms which present interatomic AIM BCPs.
Complexes are arranged in ascending order of energy.
E1 (C1)
E2 (C1)
E3 (C1)
E4 (C1)
E5 (C1)
E6 (C1)
E7 (C1)
E8 (C1)
E9 (C1)
E10 (C1)
S5
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Table S5. Multi-body analysis in kcal/mol for the CO2:(SO2)3 complexes at MP2/augcc-pVDZ computational level.
Complex
E1
E2
E3
E4
E5
E6
E7
E8
E9
E10
E11
E12
E13
E14
E15
E16
E17
E18
E19
E20
E21
E22
E23
E24
E25
E26
E27
E28
E29
E30
E31
E32
E33
E34
E35
E36
E37
E38
2E
–14.73
–14.54
–14.63
–14.37
–14.11
–14.28
–14.60
–14.12
–14.13
–14.06
–14.10
–14.12
–13.70
–13.48
–13.50
–13.76
–13.81
–13.44
–13.26
–13.51
–13.45
–13.46
–13.52
–13.46
–13.24
–12.98
–13.27
–13.25
–12.83
–12.87
–12.50
–12.03
–12.09
–11.81
–10.62
–10.26
–9.12
–9.02
3E
–1.04
–1.11
–0.97
–1.06
–1.29
–1.05
–0.62
–0.84
–0.79
–0.83
–0.63
–0.49
–0.75
–1.03
–0.97
–0.69
–0.44
–0.74
–0.89
–0.54
–0.55
–0.54
–0.43
–0.33
–0.60
–0.70
–0.26
–0.39
–0.43
–0.27
–0.35
–0.44
–0.33
–0.27
–0.43
–0.42
–0.04
–0.11
S6
4E
0.01
0.02
0.00
–0.01
0.01
0.00
–0.01
0.02
–0.01
–0.02
–0.02
–0.07
–0.02
0.06
0.05
0.11
–0.08
–0.07
0.08
0.03
0.08
0.10
0.08
0.04
0.06
0.10
–0.02
0.09
0.06
0.08
0.08
0.08
0.10
0.03
0.03
0.01
0.03
0.01
total Eint
–15.76
–15.63
–15.60
–15.44
–15.39
–15.33
–15.23
–14.94
–14.93
–14.91
–14.75
–14.68
–14.47
–14.45
–14.42
–14.34
–14.33
–14.25
–14.07
–14.02
–13.92
–13.90
–13.87
–13.75
–13.78
–13.58
–13.55
–13.55
–13.20
–13.06
–12.77
–12.39
–12.32
–12.05
–11.02
–10.67
–9.13
–9.12