Supplementary data
Excited-state proton transfer reactions of 7-azaindole with water, ammonia and mixed
water-ammonia: microsolvated dynamics simulation
Khanittha Kerdpol, Rathawat Daengngern, and Nawee Kungwan*
Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200,
Thailand
*Corresponding author. E-mail: naweekung@gmail.com.
Phone: +66-53-943341 ext 101. Fax: +66-53-892277.
S1
Table S1 Average relative ground (S0) and excited states (ππ*) free energies (kcal mol−1)
State
S0
S1
(ππ*)
N
IS1
IS2
IS3
IS4
T
N
IS1
IS2
IS3
IS4
T
M
0
29
36
7AI(solvent)1
W
A
0
0
40
38
41
41
MM
0
36
38
40
MW
0
32
35
37
7AI(solvent)2
WM
WW
WA
0
0
0
37
36
35
45
37
40
46
35
45
AW
0
31
45
41
AA
0
33
45
38
27
103
105
93
43
105
111
99
26
104
106
102
26
103
105
104
100
26
101
103
99
96
38
104
110
106
105
30
104
107
103
103
25
106
113
112
100
33
103
105
103
97
24
104
107
106
94
92
98
92
89
88
101
98
93
97
93
MMM
0
29
44
47
37
29
103
110
110
102
96
94
WWW
0
56
46
42
44
35
104
121
107
117
106
99
WWA
0
45
33
40
42
41
104
115
97
111
97
89
7AI(solvent)3
WAW
WAA
0
0
40
39
47
23
49
37
53
45
48
13
103
106
117
115
115
100
109
99
110
98
95
91
AWW
0
38
52
45
50
31
104
113
111
104
111
100
AWA
0
40
28
46
57
25
109
117
102
111
105
95
AAW
0
45
47
35
46
28
105
113
110
93
98
87
AAA
0
47
47
43
32
23
104
121
114
106
94
90
For characteristic points of each complex. M-Methanol, W-Water, and A-Ammonia.
Daengngern et al. J. Phys. Chem. A 2011 in 100 trajectories, Kungwan et al. 2014 submitted in 50 trajectories, Daengngern et al. J. Photochem.
Photobiol. A 2013 in 25 trajectories
S2
Table S2 Average time lag of the excited-state dynamics simulation
Time (fs)
COMPLEXES
7AI(solvent)1
7AI(solvent)2
7AI(solvent)3
PT1
Time lag
PT2
Time lag
PT3
Time lag
PT4
7AI(M)
71
13
84
7AI(W)
48
11
59
7AI(A)
85
39
124
7AI(MM)
68
13
81
3
84
7AI(MW)
71
12
83
2
85
7AI(WM)
46
12
58
2
60
7AI(WW)
69
1
70
8
78
7AI(WA)
96
9
105
21
126
7AI(AW)
74
40
114
22
136
7AI(AA)
84
54
138
31
169
7AI(MMM)
66
11
77
6
83
1
84
7AI(WWW)
69
4
73
6
79
11
90
7AI(WWA)
51
28
79
14
93
6
99
7AI(WAW)
69
7
76
33
109
9
118
7AI(WAA)
127
20
147
39
186
57
243
7AI(AWW)
95
39
134
5
139
7
146
7AI(AWA)
95
37
132
18
150
10
160
7AI(AAW)
81
30
111
17
128
6
134
7AI(AAA)
80
53
133
22
155
20
175
Daengngern et al. J. Phys. Chem. A 2011 in 100 trajectories, Kungwan et al. 2014 submitted in 50 trajectories, Daengngern et al. J. Photochem.
Photobiol. A 2013 in 25 trajectories
S3
πσ*
ππ*
S0
Figure S1 The plot of the relative energies and possible crossing between ππ* and πσ* states
for a selected 7AI(AAA) cluster.
Figure S2 Ground-state optimized structure of 7AI with one ammonia cluster at RIADC(2)/SVP-SV(P) level. Dashed lines show intermolecular hydrogen-bonded network.
S4
Figure S3 Snapshots representing the average over all ESTPT trajectories of the 7AI(WA)
cluster dynamics showing the time evolution of the ESTPT reaction through a hydrogenbonded network within 133 fs. Normal (N), proton transfer (PT), and tautomer (T).
S5
Figure S4 Average values over ESTPT trajectories of the 7AI(WA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and O1···H1 in black, O1–H2
and N''···H2 in red, and N''–H3 and N2···H3 in blue (b) Average relative energies of excited
stated state (S1), ground state (S0), and energy difference of S1 and S0 state (S1-S0).
S6
Figure S5 Snapshots representing the average over all ESTPT trajectories of the 7AI(AA)
clusters showing the time evolution of the ESTPT reaction through a hydrogen-bonded
network within 175 fs. Normal (N), proton transfer (PT), and tautomer (T).
S7
Figure S6 Average values over ESTPT trajectories of the 7AI(AA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and N'···H1 in black, N'–H2
and N''···H2 in red, and N''–H3 and N2···H3 in blue (b) Average relative energies of excited
stated state (S1), ground state (S0), and energy difference of S1 and S0 state (S1-S0).
S8
Figure S7 Snapshots of a selected trajectory of the 7AI(AAW) cluster dynamics showing the
hydrogen bond reorganization in mixed water-ammonia solvent following by ESTPT through
the new hydrogen-bonded network at 400 fs. Normal (N), Proton transfer (PT), and Tautomer
(T).
S9
Figure S8 Snapshots of a selected trajectory of the 7AI(AAA) cluster dynamics showing the
hydrogen bond reorganization in ammonias following by ESDPT through the new hydrogenbonded network at 464 fs. Normal (N), Proton transfer (PT), and Tautomer (T).
S10
Figure S9 Snapshots of the 7AI(WWA) clusters dynamics showing the time evolution of the
ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer (PT),
and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S11
Figure S10 Average values over ESQPT trajectories of the 7AI(WWA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and O1···H1 in black, O1–H2
and O3···H2 in red, O3–H3 and N''···H3 in blue, and N''–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S12
Figure S11 Snapshots of the 7AI(WAW) clusters dynamics showing the time evolution of
the ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer
(PT), and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S13
Figure S12 Average values over ESQPT trajectories of the 7AI(WAW) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and O1···H1 in black, O1–
H2 and N'''···H2 in red, N'''–H3 and O2···H3 in blue, and O2–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S14
Figure S13 Snapshots of the 7AI(WAA) clusters dynamics showing the time evolution of the
ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer (PT),
and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S15
Figure S14 Average values over ESQPT trajectories of the 7AI(WAA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and O1···H1 in black, O1–
H2 and N'''···H2 in red, N'''–H3 and N''···H3 in blue, and N''–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S16
Figure S15 Snapshots of the 7AI(AWW) cluster dynamics showing the time evolution of the
ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer (PT),
and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S17
Figure S16 Average values over ESQPT trajectories of the 7AI(AWW) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and N'···H1 in black, N'–H2
and O3···H2 in red, O3–H3 and O2···H3 in blue, and O2–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S18
Figure S17 Snapshots of the 7AI(AWA) cluster dynamics showing the time evolution of the
ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer (PT),
and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S19
Figure S18 Average values over ESQPT trajectories of the 7AI(AWA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and N'···H1 in black, N'–H2
and O3···H2 in red, O3–H3 and N''···H3 in blue, and N''–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S20
Figure S19 Snapshots of the 7AI(AAA) cluster dynamics showing the time evolution of the
ESQPT reaction through the hydrogen-bonded network. Normal (N), Proton transfer (PT),
and Tautomer (T). Values correspond to the average over all ESQPT trajectories.
S21
Figure S20 Average values over ESQPT trajectories of the 7AI(AAA) clusters. (a) Average
breaking and forming of bonds showing time evolution. N1–H1 and N'···H1 in black, N'–H2
and N'''···H2 in red, N'''–H3 and N''···H3 in blue, and N''–H4 and N2···H4 in green (b)
Average relative energies of excited stated state (S1), ground state (S0), and energy difference
of S1 and S0 state (S1-S0).
S22
Figure S21 Average relative energies (kcal.mol-1) of the ground (S0) and the excited states
(ππ*) of 7AI(solvent)1: 7AI(M), 7AI(W) and 7AI(A).
S23
Figure S22 Average relative energies (kcal.mol-1) of the ground (S0) and the excited states
(ππ*) of 7AI(solvent)2: 7AI(MM), 7AI(MW), 7AI(WM), 7AI(WW), 7AI(WA), 7AI(AW)
and 7AI(AA).
S24
Figure S23 Average relative energies (kcal.mol-1) of the ground (S0) and the excited states
(ππ*) of 7AI(solvent)3: 7AI(MMM), 7AI(WWW), 7AI(WWA), 7AI(WAW), 7AI(WAA),
7AI(AWW), 7AI(AWA), 7AI(AAW) and 7AI(AAA).
S25