1
Supporting Information
Are the reduction and oxidation properties of nitro-compoundsdissolved in water
and adsorbed by silica surface different?
An DFT M05-2X computational study
Liudmyla K. Sviatenko,1,2 Olexandr Isayev,3 Leonid Gorb,4 Frances C. Hill,5 Danuta Leszczynska,6 Jerzy
Leszczynski1,*
1
Interdisciplinary Nanotoxicity Center, Department of Chemistry and Biochemistry, Jackson State University,
Jackson, MS, USA, 39217
2
Department of Organic Chemistry, Oles Honchar Dnipropetrovsk National University, Dnipropetrovsk,
Ukraine, 49000
3
Division of Chemical Biology and Medicinal Chemistry, UNC Eshelman School of Pharmacy, University of
North Carolina at Chapel Hill, NC, USA, 27599-7363
4
Badger Technical Services, Inc., 4815 Bradford Dr, NW Huntsville, AL, USA, 35805
5
US Army ERDC, Vicksburg, MS, USA, 39180
6
Interdisciplinary Nanotoxicity Center, Department of Civil and Environmental Engineering, Jackson State
University, Jackson, MS, USA, 39217
Table S1. M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds
including H∙∙∙Y, X∙∙∙Y distances (Å) and X-H∙∙∙Y angles (degree) for adsorbed DNAN, its anion- and
cation-radical.
Table S2. M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds
including H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed DNT, its anion- and
cation-radical.
Table S3. M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds
including H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed NTO, its anion- and
cation-radical.
Table S4. M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds
including H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed TNT, its anion- and
cation-radical.
Fig. S1. M05/tzvp and SMD/PCM(Pauling)/M05/tzvp levels calculated EA and IP, eV.
0
0
Fig. S2. M05/tzvp and SMD/PCM(Pauling)/M05/tzvp levels calculated ∆𝐸𝑟𝑒𝑑
and ∆𝐸𝑜𝑥
, eV.
Fig. S3. The optimized structures of nitrocompounds adsorbed on a model of the (001) α-quartz
surface (grey – carbon, light grey – hydrogen, red – oxygen, blue – nitrogen, cyan – silica).
2
Table S1
M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds including
H∙∙∙Y, X∙∙∙Y distances (Å) and X-H∙∙∙Y angles (degree) for adsorbed DNAN, its anion- and cationradical.
Bond
HB1
HB2
HB3
HB4
HB5
HB6
HB7
HB8
HB9
Bond type
(N2-)O(1)∙∙∙H-O(1)
(N2-)O(2)∙∙∙H-O(1)
C7-H∙∙∙O(1)
C7-O∙∙∙H-O
(N2-)O(1)∙∙∙H-O(2)
(N2-)O(1)∙∙∙H-O(3)
(N2-)O(2)∙∙∙H-O(3)
C7-H∙∙∙O(2)
C6-H∙∙∙O
DNAN
X∙∙∙Y
2.98
2.96
3.70
–
–
–
–
–
–
X∙∙∙H
2.13
2.27
2.67
–
–
–
–
–
–
XHY
144.9
127.8
157.5
–
–
–
–
–
–
DNAN-.
X∙∙∙Y
2.76
2.73
–
2.89
2.95
3.36
2.78
–
–
X∙∙∙H
1.87
1.76
–
1.97
2.12
2.66
1.81
–
–
XHY
149.6
165.8
–
158.6
143.2
128.9
171.7
–
–
DNAN+.
X∙∙∙Y
–
–
3.29
–
–
–
–
3.02
3.47
X∙∙∙H
–
–
2.21
–
–
–
–
2.53
2.46
XHY
–
–
173.1
–
–
–
–
106.5
155.8
Table S2
M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds including
H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed DNT, its anion- and cation-radical.
Bond
HB1
HB2
HB3
HB4
HB5
HB6
HB7
HB8
HB9
HB10
Bond type
X∙∙∙H
2.07
2.15
2.28
–
–
–
–
–
–
–
(N2-)O(1)∙∙∙H-O(1)
(N4-)O(1)∙∙∙H-O(1)
(N4-)O(2)∙∙∙H-O(1)
(N4-)O(1)∙∙∙H-O(2)
(N4-)O(2)∙∙∙H-O(2)
C7-H(1)∙∙∙O
(N2-)O(2)∙∙∙H-O(3)
(N4-)O(2)∙∙∙H-O(3)
C7-H(2)∙∙∙O
C6-H∙∙∙O
DNT
X∙∙∙Y
2.88
3.09
3.16
–
–
–
–
–
–
–
XHY
140.8
165.8
151.1
–
–
–
–
–
–
–
X∙∙∙H
1.95
–
–
1.79
1.83
2.63
–
–
–
–
DNT-.
X∙∙∙Y
2.89
–
–
2.77
2.80
3.55
–
–
–
–
XHY
165.3
–
–
169.5
166.8
141.9
–
–
–
–
X∙∙∙H
–
–
–
–
–
–
2.13
2.67
2.64
2.66
DNT+.
X∙∙∙Y
–
–
–
–
–
–
3.03
3.06
3.43
3.24
XHY
–
–
–
–
–
–
155.8
105.4
129.3
112.8
Table S3
M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds including
H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed NTO, its anion- and cation-radical.
Bond
HB1
HB2
HB3
Bond type
C3-O∙∙∙H-O
N5-O∙∙∙H-O
N4-H∙∙∙O*
X∙∙∙H
1.72
1.99
2.14
NTO
X∙∙∙Y
2.69
2.93
3.06
* N4∙∙∙H-O bond type in case of NTO+.
XHY
167.7
166.8
149.8
X∙∙∙H
1.66
1.20
2.19
NTO-.
X∙∙∙Y
2.64
2.40
3.05
XHY
172.2
178.7
142.0
X∙∙∙H
–
–
1.81
NTO+.
X∙∙∙Y
–
–
2.77
XHY
–
–
166.0
3
Table S4
M05/tzvp level calculated geometrical characteristics of adsorbate-adsorbent H-bonds including
H∙∙∙Y, X∙∙∙Y distances (A) and X-H∙∙∙Y angles (degree) for adsorbed TNT, its anion- and cation-radical.
Bond
HB1
HB2
HB3
HB4
HB5
HB6
HB7
HB8
Bond type
(N6-)O∙∙∙H-O
C7-H∙∙∙O
(N2-)O∙∙∙H-O
(N4-)O(1)∙∙∙H-O(1)
(N4-)O(1)∙∙∙H-O(2)
(N4-)O(2)∙∙∙H-O(1)
(N4-)O(2)∙∙∙H-O(2)
C3-H∙∙∙O
X∙∙∙H
2.70
2.53
–
–
–
–
–
–
TNT
X∙∙∙Y
3.14
3.52
–
–
–
–
–
–
XHY
109.2
151.5
–
–
–
–
–
–
X∙∙∙H
–
–
2.03
2.33
2.59
2.36
1.83
2.60
TNT-.
X∙∙∙Y
–
–
2.93
3.09
3.27
3.27
2.79
3.13
XHY
–
–
154.2
135.2
128.3
157.0
169.7
109.6
X∙∙∙H
2.66
–
–
–
–
–
–
–
TNT+.
X∙∙∙Y
3.10
–
–
–
–
–
–
–
Electron attaching free energy consists of electron affinity and difference between entropy
terms of anion-radical and neutral molecule.
0
0 (𝑅 −. )
0 (𝑂))
∆𝐺𝑟𝑒𝑑,𝑔𝑎𝑠
= 𝐸𝐴𝑔𝑎𝑠 − 𝑇 ∙ (𝑆𝑔𝑎𝑠
− 𝑆𝑔𝑎𝑠
0
0
0
(𝑅 −. ) − 𝑆𝑎𝑑𝑠
(𝑂))
∆𝐺𝑟𝑒𝑑,𝑎𝑑𝑠
= 𝐸𝐴𝑎𝑑𝑠 − 𝑇 ∙ (𝑆𝑎𝑑𝑠
0
0
0
−.
∆𝐺𝑟𝑒𝑑,𝑠𝑜𝑙𝑣 = 𝐸𝐴𝑠𝑜𝑙𝑣 − 𝑇 ∙ (𝑆𝑠𝑜𝑙𝑣 (𝑅 ) − 𝑆𝑠𝑜𝑙𝑣 (𝑂))
0 (𝑅 −. )
𝑆𝑔𝑎𝑠
– gas-phase entropy of reduced form (anion-radical)
0 (𝑂)
𝑆𝑔𝑎𝑠
– gas-phase entropy of oxidized form (neutral molecule)
0
−.
𝑆𝑎𝑑𝑠 (𝑅 ) – entropy of adsorbed reduced form (anion-radical)
0
(𝑂) – entropy of adsorbed oxidized form (neutral molecule)
𝑆𝑎𝑑𝑠
0
𝑆𝑠𝑜𝑙𝑣 (𝑅 −. ) – entropy of solvated reduced form (anion-radical)
0
(𝑂) – entropy of solvated oxidized form (neutral molecule)
𝑆𝑠𝑜𝑙𝑣
Electron detachment free energy consists of ionization potential and difference between
entropy terms of cation-radical and neutral molecule.
0
0 (𝑂 +. )
0 (𝑅))
∆𝐺𝑜𝑥,𝑔𝑎𝑠
= 𝐼𝑃𝑔𝑎𝑠 − 𝑇 ∙ (𝑆𝑔𝑎𝑠
− 𝑆𝑔𝑎𝑠
0
0
0
(𝑂+. ) − 𝑆𝑎𝑑𝑠
(𝑅))
∆𝐺𝑜𝑥,𝑎𝑑𝑠
= 𝐼𝑃𝑎𝑑𝑠 − 𝑇 ∙ (𝑆𝑎𝑑𝑠
0
0
0
(𝑂+. ) − 𝑆𝑠𝑜𝑙𝑣
(𝑅))
∆𝐺𝑜𝑥,𝑠𝑜𝑙𝑣
= 𝐼𝑃𝑠𝑜𝑙𝑣 − 𝑇 ∙ (𝑆𝑠𝑜𝑙𝑣
0 (𝑂 +. )
𝑆𝑔𝑎𝑠
– gas-phase entropy of oxidized form (cation-radical)
0 (𝑅)
𝑆𝑔𝑎𝑠
– gas-phase entropy of reduced form (neutral molecule)
0
+. )
(𝑂
𝑆𝑎𝑑𝑠
– entropy of adsorbed oxidized form (cation-radical)
0
(𝑅) – entropy of adsorbed reduced form (neutral molecule)
𝑆𝑎𝑑𝑠
0
(𝑂+. ) – entropy of solvated oxidized form (cation-radical)
𝑆𝑠𝑜𝑙𝑣
0
(𝑅) – entropy of solvated reduced form (neutral molecule)
𝑆𝑠𝑜𝑙𝑣
XHY
108.5
–
–
–
–
–
–
–
4
EA, eV
-2
DNANgas
DNANads
DNTgas
DNTads
11
NTOgas
TNTgas
NTOads
DNTsolv
-4
NTOsolv
DNANgas
9
TNTads
-3
DNANsolv
10
IP, eV
-1
8
DNANads
DNTgas
DNANsolv
6
TNTgas
TNTads
DNTads
7
TNTsolv
NTOgas
NTOads
DNTsolv
NTOsolv
TNTsolv
5
-5
Fig. S1. M05/tzvp and SMD/PCM(Pauling)/M05/tzvp levels calculated EA and IP, eV.
0
DNTsolv
DNTgas
TNTads
NTOads
DNANads
TNTgas
-2
DNTads
DNANgas
DNTgas
TNTgas
6
5
-1
-3
TNTsolv
Eox, eV
Ered, eV
DNANsolv
NTOsolv
NTOgas
DNANgas
TNTads
DNTads
4
DNANads
NTOads
3
2
NTOgas
DNTsolv
NTOsolv
DNANsolv
1
0
0
Fig. S2. M05/tzvp and SMD/PCM(Pauling)/M05/tzvp levels calculated ∆𝐸𝑟𝑒𝑑
and ∆𝐸𝑜𝑥
, eV.
TNTsolv
5
DNANads
DNANads—
DNANads+
DNTads
DNTads—
DNTads+
NTOads
NTOads—
NTOads+
6
TNTads
TNTads—
TNTads+
Fig. S3. The optimized structures of nitrocompounds adsorbed on a model of the (001) α-quartz
surface (grey – carbon, light grey – hydrogen, red – oxygen, blue – nitrogen, cyan – silica).