Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is © the Owner Societies 2016
Electronic Supplementary Information Examining Structural Evolution of Bicarbonate-Water Clusters: Insights
from
Photoelectron
Spectroscopy,
Basin-Hopping
Structural Search, and Comparison with Available IR Spectra Studies Hui Wen,1,2 Gao-Lei Hou,2,Yi-Rong Liu,1 Xue-Bin Wang, *,2 Wei Huang*,1,3
1Laboratory
of Atmospheric Physico-Chemistry, Anhui Institute of Optics & Fine Mechanics,
Chinese Academy of Sciences, Hefei, Anhui 230031, China 2Physical
Sciences Division, Pacific Northwest National Laboratory, P. O. Box 999, MS K8-
88, Richland, Washington 99352, USA 3School
of Environmental Science & Optoelectronic Technology, University of Science and
Technology of China, Hefei, Anhui 230026, China
*E-mails:
[email protected],
[email protected]
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Table S1. Optimized structures and bond parameters of HCO3−(H2O)2 under different DFT functionals with same basis set (6-311++G**), and compared with MP2 method.
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Table S2. Top 12 occupied molecular orbital energies of HCO3–(H2O)n, n=0-13
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3- a 0.000 (3-I)
3- b 0.699 (3-III)
3- c 1.104
3- d 1.104
3- e 1.143 (3-II)
3- f 1.591
3- g 1.591
3- h 1.739
3- i 2.369
Figure S1. Low-lying isomers of HCO3−(H2O)3 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses.
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4- a 0.000 (4-I)
4- b 0.621(4-II)
4- c 0.723
4- d 1.428
4- e 1.603 (4-III)
4- f 1.816
Figure S2. Low-lying isomers of HCO3−(H2O)4 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses.
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5- a 0.000 (5-III)
5- b 0.267 (5-II)
5- c 0.353
5- d 1.406 (5-I)
5- e 1.936
5- f 2.338
5- g 3.209
5- h 3.801
Figure S3. Low-lying isomers of HCO3−(H2O)5 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses.
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6- a 0.000
6- b 1.238
6- c 2.395
6- d 2.547
6- e 2.685
6- f 2.858
6- g 2.977
6- h 3.586
6- i 4.015
6- j 4.311 (6-I)
6- k 4.819
6- l 5.036 (6-II)
6- m 8.897 Figure S4. Low-lying isomers of HCO3−(H2O)6 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses.
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7- a 0.000
7- b 0.358
7- c 0.370 (7-I)
7- d 0.898
7- e 1.020
7- f 1.324
7- g 1.428
7- h 1.583
7- i 1.689
7- j 2.611 (7-III)
7- k 2.852
7- l 2.865
7- m 3.033
7- n 4.076 (7-II)
7- o 8.174
Figure S5. Low-lying isomers of HCO3−(H2O)7 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses.
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8- a 0.000
8- b 1.304
8- c 1.482
8- d 1.892
8- e 2.194
8- f 2.203
8- g 2.690
8- h 2.814
8- i 3.005
8- j 3.018
8- k 3.245 (8 -II)
8- l 3.309
8- m 3.332
8- n 3.789
8- o 4.211
8- p 5.840 (8-III)
8- q 7.317 (8-I)
Figure S6. Low-lying isomers of HCO3−(H2O)8 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated. The structures that are similar to those in the work of Neumark & Asmis are also labeled in parentheses. 9 / 35
9- a 0.000
9- b 0.688
9- c 1.037
9- d 1.096
9- e 1.202
9- f 1.598
9- g 1.635
9- h 2.024
9- i 2.232
9- j 2.275
9- k 2.349
9- l 2.350
9- m 2.435
9- n 2.639
9- o 2.737
Figure S7. Low-lying isomers of HCO3−(H2O)9 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated.
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10- a 0.000
10- b 0.117
10- c 0.775
10- d 0.804
10- e 2.066
10- f 2.266
10- g 2.320
10- h 2.406
10- i 2.472
10- j 2.481
10- k 2.664
10- l 2.815
10- m 3.175
10- n 6.420
10- o 9.071
10- p 9.833
Figure S8. Low-lying isomers of HCO3−(H2O)10 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated.
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11- a 0.000
11- b 1.406
11- c 1.756
11- d 1.856
11- e 2.110
11- f 2.975
11- g 3.049
11- h 3.092
11- i 4.039
11- j 4.281
11- k 4.344
11- l 5.152
11- m 6.364
11- n 9.334
11- o 9.604
Figure S9. Low-lying isomers of HCO3−(H2O)11 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated.
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12- a 0.000
12- b 0.050
12- c 0.056
12- d 1.099
12- e 1.157
12- f 1.409
12- g 2.364
12- h 2.663
12- i 3.182
12- j 3.445
12- k 4.016
12- l 4.300
Figure S10. Low-lying isomers of HCO3−(H2O)12 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated.
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13- a 0.000
13- b 4.275
13- c 4.915
13- d 5.241
13- e 5.584
13- f 5.611
13- g 5.711
13- h 5.882
13- i 6.687
13- j 6.856
13- k 7.053
13- l 7.916
Figure S11. Low-lying isomers of HCO3−(H2O)13 under B3LYP/6-311++G(3df, 3pd) level of theory, relative energies (in kcal/mol) are indicated.
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Figure S12. The stick density of states (DOS) spectra of the minimum energy isomer of HCO3−(H2O)1-6.
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Figure S13. The stick density of states (DOS) spectra of HCO3−(H2O)7-12.
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Figure S14. Simulated PES spectra of HCO3−(H2O)n, n=1-4 accompany with structures, and relative energies (in kcal/mol) of the low-lying isomers at the B3LYP/6-311++(3df,3pd) level of theory, marked n-a and n-b, respectively. Any structures that are similar to those in the work of Neumark and Asmis are also labeled in red.
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Figure S15. Simulated PES spectra of HCO3−(H2O)n, n=5-8 accompany with structures, and relative energies (in kcal/mol) of the low-lying isomers at the B3LYP/6-311++(3df,3pd) level of theory, marked n-a and n-b, respectively.
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Figure S16. Simulated PES spectra of HCO3−(H2O)n, n=9-12 accompany with structures, and relative energies (in kcal/mol) of the low-lying isomers at the B3LYP/6-311++(3df,3pd) level of theory, marked n-a and n-b, respectively.
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2000
1-c 1-III 1.32 kcal/mol
1-a 1-I 0.0 kcal/mol
1500
1000
500
0
1600
600
800
1-b 1-II 0.98 kcal/mol
1400 1200 1000
1000
1200
1400
1600
1800
600
800
1000
1200
1400
1600
1800
1000
1200
1400
1600
1800
1-d 1.32 kcal/mol
800 600 400 200 0 2500
600
800
1000
1200
1400
1600
1800
1000
1200
1400
1600
1800
600
800
1-e 2.31 kcal/mol
2000 1500 1000 500 0 600
800
Fig. S17 Experimental (copied from Ref. 20) and theoretical infrared spectra of HCO3−(H2O)1, clusters.
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2000 2000
2-a 2-I 0.00 kcal/mol
1500 1000
3-a 3-I 0.00 kcal/mol
1500
1000
500
500
0
0
600
600
800
1500
1000
1200
1400
1600
1500
2-b 2-III 0.16 kcal/mol
1000
800
1000
1200
1400
1600
1800
1800
3-b 3-III 0.70 kcal/mol
1000
500
500
0
0 600
800
1000
1200
1400
1600
1800
1600
1800
600
800
1000
1200
1400
1600
1800
4-a 4-I 0.00 kcal/mol
600
800
1000
1200
1400
4-b 4-II 0.62 kcal/mol
600
800
1000
1200
1400
1600
1800
Fig. S18 Experimental (copied from Ref. 20) and theoretical infrared spectra of HCO3−(H2O)n, n=2-4 clusters.
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5-a 5-III 0.00 kcal/mol
6-a 0.00 kcal/mol
5-d 5-I 1.41 kcal/mol
6-j 6-I 4.31 kcal/mol
5-h 3.80 kcal/mol
Fig. S19 Experimental (copied from Ref. 20) and theoretical infrared spectra of HCO3−(H2O)5 and HCO3−(H2O)6 clusters.
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7-a 0.00 kcal/mol
7-c 7-I 0.37 kcal/mol
7-b 0.36 kcal/mol
Fig. S20 Experimental (copied from Ref. 20) and theoretical infrared spectra of HCO3−(H2O)7 clusters.
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8-a 0.00 kcal/mol
8-c 1.48 kcal/mol
8-q 8-I 7.32 kcal/mol
Fig. S21 Experimental (copied from Ref. 20) and theoretical infrared spectra of HCO3−(H2O)8 clusters.
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HCO3−(H2O)1
800
HCO3−(H2O)4
2000
600
1500
400
1000
200
500
1-a 0.00 (1-I)
4-a 0.00 (4-I)
0
0 2600
2800
3000
3200
3400
3600
2600
3800
2800
3000
3200
3400
3600
3800
3400
3600
3800
3400
3600
3800
3400
3600
3800
3200
3400
3600
3800
3200
3400
3600
3800
1600 1500
1400 1200 1000
1000
800 600 500
1-b 0.98 (1-II)
400 200
4-b 0.62(4-II)
0 3000 2500
0 2600
2800
3000
3200
3400
3600
3800
−
HCO3 (H2O)2
2600
2800
3000
3200
−
HCO3 (H2O)5
2000
1500
2000 1500
1000
1000 500
500
2-a 0.00 (2-II)
0
5-a 0.00 (5-III)
0 2600
2800
3000
3200
3400
3600
3800
2600
2800
3000
3200
1600 1500
1400 1200 1000
1000
800 600 500
400
2-b 0.16 (2-I)
200
5-b 0.27 (5-II)
0
0 2600
2800
3000
3200
3400
3600
3800
−
HCO3 (H2O)3
2000
2600 2500
2800
3000
3200
−
HCO3 (H2O)6
2000
1500
1500 1000 1000 500
500
3-a 0.00 (3-I)
0 2600
2800
3000
3200
6-a 0.00
0 3400
3600
3800
2600
2800
3000
3000
2500
2500
2000
2000 1500 1500 1000 1000 500
500
3-b 0.70 (3-III)
0 2600
2800
3000
3200
6-j 4.31 (6-I)
0 3400
3600
3800
2600
2800
3000
Fig. S22 Simulated IR spectra (O-H stretching mode: 2600-3900 cm-1) of HCO3−(H2O)n, n=16 clusters at B3LYP/6-311++G(3df, 3pd). 25 / 35
HCO3−(H2O)7
3500
HCO3−(H2O)9
3000
3000
2500
2500
2000
2000 1500 1500 1000
1000 500
500
7-a 0.00
0 2600
2800
9-a 0.00
0 3000
3200
3400
3600
2600
3800
4000
2500
3000
2000
2800
3000
3200
3400
3600
3800
3200
3400
3600
3800
3200
3400
3600
3800
3200
3400
3600
3800
1500
2000 1000
1000
500
7-c 0.37 (7-I)
0 2600
2800
3000
3200
3400
3600
3800
−
HCO3 (H2O)8
3000 2500
9-b 0.69
0 2500 2600
−
3000
HCO3 (H2O)10
2000
2000
2800
1500
1500
1000 1000
500
500
8-a 0.00
10-a 0.00
0
0 2600
2800
3000
3200
3400
3600
3800
2600
2800
3000
5000
3000
4000 3000
2000
2000
1000
1000
10-b 0.12
8-q 7.32 (8-I) 0
0 2600
2800
3000
3200
3400
3600
3800
2600
2800
3000
Fig. S23 Simulated IR spectra (O-H stretching mode: 2600-3900 cm-1) of HCO3−(H2O)n, n=710 clusters at B3LYP/6-311++G(3df, 3pd).
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HCO3−(H2O)11
HCO3−(H2O)13
5000
3000
4000 3000
2000
2000 1000 1000
11-a 0.00 0 3000
13-a 0.00
0 2600
2800
3000
3200
3400
3600
3800
2600
2800
3000
3200
3400
3600
3800
3200
3400
3600
3800
3200
3400
3600
3800
3200
3400
3600
3800
4000
2500
3000
2000 1500
2000
1000 1000
500
11-b 1.41
13-b 4.26 0
0 2600 4000
2800
3000
3200
3400
3600
3800
−
HCO3 (H2O)12
5000
2600
2800
3000
4000
3000 3000
2000 2000
1000
1000
13-c 4.92
12-a 0.00
0
0
2600
2800
3000
3200
3400
3600
3800
2600
4000
2800
3000
6000 5000
3000
4000 2000
3000 2000
1000
12-b 0.05
1000
0
13-d 5.24
0 2600
2800
3000
3200
3400
3600
3800
2600
2800
3000
Fig. S24 Simulated IR spectra (O-H stretching mode: 2600-3900 cm-1) of HCO3−(H2O)n, n=11-13 clusters at B3LYP/6-311++G(3df, 3pd).
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n=1
n=6
n=11
n=2
n=7
n=4
n=3
n=8
n=12
n=9
n=5
n=10
n=13 −(H
Fig. S25 The most probable structures of HCO3 2O)n, n=1-13 clusters determined by comparison of NIPE spectra, BH structural search and available IR spectra.
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Fig. S26 Molecular orbitals of the minimum energy isomer of HCO3−(H2O)1.
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Fig. S27 Molecular orbitals of the minimum energy isomer of HCO3−(H2O)2.
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Fig. S28 Molecular orbitals of the minimum energy isomer of HCO3−(H2O)3.
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Fig. S29 Molecular orbitals of the minimum energy isomer of HCO3−(H2O)4.
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Fig. S30 Molecular orbitals of the minimum energy isomer of HCO3−(H2O)10.
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Fig. S31 Symbols and labels of each atom of HCO3−(H2O)10.
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9-a 0.00
10-a 0.00
11-a 0.00
12-a 0.00
13-a 0.00
9-b 0.69
9-c 1.04
9-d 1.10
9-e 1.20
10-b 0.12
10-c 0.78
10-d 0.80
10-e 2.07
11-b 1.41
11-c 1.76
11-d 1.86
11-e 2.11
12-b 0.05
13-b 4.26
12-c 0.06
13-c 4.92 −(H
12-d 1.10
13-d 5.24
12-e 1.16
13-e 5.58
Figure S32. Top five low-lying isomers of HCO3 2O)n (n = 9-13) at B3LYP/6-311++G(3df, 3pd) level of theory. Relative energies (in kcal/mol) are indicated.
35 / 35