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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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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

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1-b 1-II 0.98 kcal/mol

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1-d 1.32 kcal/mol

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1-e 2.31 kcal/mol

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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

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3-a 3-I 0.00 kcal/mol

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2-b 2-III 0.16 kcal/mol

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3-b 3-III 0.70 kcal/mol

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4-a 4-I 0.00 kcal/mol

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4-b 4-II 0.62 kcal/mol

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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

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HCO3−(H2O)4

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1-a 0.00 (1-I)

4-a 0.00 (4-I)

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1-b 0.98 (1-II)

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4-b 0.62(4-II)

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HCO3 (H2O)2

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HCO3 (H2O)5

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2-a 0.00 (2-II)

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2-b 0.16 (2-I)

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5-b 0.27 (5-II)

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HCO3 (H2O)3

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HCO3 (H2O)6

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3-a 0.00 (3-I)

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6-a 0.00

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3-b 0.70 (3-III)

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6-j 4.31 (6-I)

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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

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HCO3−(H2O)9

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7-a 0.00

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7-c 0.37 (7-I)

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HCO3 (H2O)8

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9-b 0.69

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HCO3 (H2O)10

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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

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11-b 1.41

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13-c 4.92

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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.

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