Supporting Information:
Table S.1 Calculated Vibrational Frequencies of Gas Phase species.
Frequencies [cm-1]
Species
H2
4430
CO
2205
CO2
2469, 1351, 629, 623
H 2O
3940, 3825, 1575
HCOOH
3693, 2980, 1725, 1281, 1025, 996, 925, 682, 402
1
Table S.2 Calculated PW91 Binding Energies (BE), with (w) and without (w/o) ZPE corrections, and
Vibrational Frequencies of Adsorbed Species at their Preferred Adsorption Site on Au(111).
Species
Adsorption
Site
Frequencies [cm-1]
BE / eV
W/O
W
ZPE
ZPE
H*
fcc
-2.04
-1.90
879.4, 681.2, 596.5
O*
fcc
-2.46
-2.41
394.2, 250.0, 247.5
OH*
bridge
-1.56
-1.36
3766.3, 576.5, 546.6, 307.3, 165.7, 125.6
H2O*
top
-0.16
-0.10
3884.4, 3773.4, 1551.2, 339.2, 260.4, 244.4, 71.0, 66.4, 59.7
CO*
top
-0.26
-0.21
2138.5, 229.6, 222.1, 214.2, 82.2, 50.4
CO2*
physisorbed
-0.05
-0.02
2458.8, 1349.6, 635.8, 634.3, 144.2, 117.6, 49.2, 35.5, 21.2
HCO*
top
-1.20
-1.05
2903.5, 1814.8, 1138.2, 726.9, 458.5, 263.2, 128.4, 121.0, 97.8
HCOO**
top-top
-1.79
-1.69
COOH*
top
-1.35
-1.27
COOHcis*
top
-1.30
-1.22
HCOOH*
top
-0.16
-0.10
2927.4, 1575.7, 1303.6, 1285.0, 968.5, 729.4, 289.4, 263.3,
244.8, 107.4, 91.3, 64.6
3446.8, 1824.6, 1200.6, 1104.1, 625.9, 588.6, 447.5, 268.6,
208.7, 126.9, 106.9, 85.7
3622.3, 1765.6, 1230.1, 1042.2, 627.5, 618.6, 399.0, 267.4,
224.9, 103.0, 96.9, 59.3
3437.4, 3006.4, 1748.5, 1343.8, 1273.0, 1117.5, 998.4, 663.0,
619.7, 144.3, 100.8, 88.8, 77.9, 59.3, 26.7
2
Table S.3 Calculated PW91 Binding Energies (BE), with (w) and without (w/o) ZPE corrections, and
Vibrational Frequencies of Adsorbed Species at their Preferred Adsorption Site on Au(100).
Species
Adsorption
Site
Frequencies [cm-1]
BE / eV
W/O
W
ZPE
ZPE
H*
bridge
-2.22
-2.06
1126.5, 1055.9, 361.0
O*
hollow
-2.73
-2.69
250.6, 140.9, 131.8
OH*
bridge
-2.18
-1.96
3789.3, 727.2, 556.4, 317.8, 272.3, 138.5
H2O*
top
-0.20
-0.14
3875.4, 3760.3, 1547.9, 348.3, 334.8, 147.2, 86.9, 63.9, 30.6
CO*
bridge
-0.68
-0.62
1970.6, 293.5, 283.6, 257.1, 224.6, 88.4
CO2*
physisorbed
-0.05
-0.02
2455.7, 1350.7, 627.1, 612.1, 116.5, 96.9, 92.1, 65.5, 51.6
HCO*
top
-1.41
-1.26
2868.4, 1803.2, 1167.5, 731.7, 479.6, 254.3, 130.7, 126.8, 116.8
HCOO**
top-top
-2.13
-2.02
COOH*
top
-1.58
-1.48
COOHcis*
top
-1.57
-1.48
HCOOH*
top
-0.22
-0.16
2934.5, 1584.7, 1315.2, 1303.5, 976.1, 725.9, 289.1, 281.6,
257.0, 95.1, 87.8, 49.8
3763.8, 1671.2, 1199.4, 1125.6, 665.8, 573.9, 432.3, 248.7,
232.5, 147.3, 93.1, 55.3
3617.3, 1617.3, 1258.0, 1098.3, 652.1, 645.9, 395.5, 261.6,
233.1, 147.1, 59.9, 57.4
3273.3, 3014.9, 1732.3, 1342.3, 1284.7, 1131.4, 1000.6, 702.5,
629.3, 170.2, 135.2, 90.4, 88.5, 64.2, 51.4
3
Table S.4 Calculated PW91 Binding Energies (BE), with (w) and without (w/o) ZPE corrections, and
Vibrational Frequencies of Adsorbed Species at their Preferred Adsorption Site on Au(211).
Species
Adsorption
Site
Frequencies [cm-1]
BE / eV
W/O
W
ZPE
ZPE
H*
bridge
-2.27
-2.11
1131.7, 1044.7, 393.4
O*
bridge
-2.86
-2.80
434.9, 398.2, 132.4
OH*
bridge
-2.29
-2.07
3804.9, 730.3, 568.7, 309.3, 262.0, 144.0
H2O*
Off-top
-0.25
-0.20
3864.1, 3711.8, 1547.0, 414.1, 335.1, 144.2, 111.0, 71.3, 55.0
CO*
bridge
-0.73
-0.67
1967.7, 313.5, 274.5, 250.5, 212.8, 121.2
CO2*
physisorbed
-0.06
-0.05
2454.7, 1349.5, 626.1, 622.1, 111.7, 77.2, 41.6, 35.7, 20.8
HCO*
top
-1.53
-1.38
2876.1, 1808.7, 1176.5, 733.1, 487.3, 220.7, 97.3, 94.5, 82.2
HCOO**
top-top
-2.29
-2.19
COOH*
top
-1.68
-1.58
COOHcis*
top
-1.68
-1.59
HCOOH*
top
-0.28
-0.21
2951.7, 1589.5, 1316.7, 1301.1, 971.1, 726.0, 282.8, 277.8,
253.9, 99.4, 93.0, 87.1
3764.5, 1637.8, 1209.8, 1134.0, 679.3, 578.1, 436.4, 278.5,
222.0, 157.8, 111.6, 93.1
3604.6, 1578.9, 1268.5, 1117.7, 664.6, 660.1, 406.8, 282.9,
234.5, 167.6, 114.8, 105.9
3378.6, 3023.9, 1719.3, 1342.2, 1286.0, 1117.7, 998.9, 702.7,
631.7, 179.4, 158.4, 93.9, 79.6, 58.1, 45.6
4
Table S.5 PW91 reaction energies (∆E), activation energy barriers (EA) for the elementary steps considered in
the HCOOH decomposition reaction network on Au(111), with (w) and without (w/o) ZPE corrections. All
the values are relative to the infinite separation of species in the initial/final states.
Adsorbate
#
Reaction
Interaction / eV
∆E / eV
EA / eV
W/O
W
W/O
W
ZPE
ZPE
ZPE
ZPE
IS / FS
1
HCOOH + *  HCOOH*
-/-
-0.16
-0.10
2
HCOOH*  HCOOHpa*
-/-
0.24
0.24
0.60
0.55
3
HCOOH* + 2*  HCOO** + H*
- / -0.06
1.02
0.86
1.46
1.29
4
HCOOHpa* + *  COOH* + H*
- / -0.03
0.96
0.80
1.44
1.22
5
HCOOH* + *  HCO* + OH*
- / -0.15
2.42
2.32
2.27
2.16
6
HCOO**  CO2* + H*
- / 0.00
-0.21
-0.35
0.86
0.80
7
HCOO** + H*  H2 + CO2* + 2*
-0.06 / 0.00
-0.71
-0.84
1.08
0.99
8
COOH* + *  CO2* + H*
- / 0.00
-0.39
-0.54
0.74
0.54
9
COOH*  COOHcis*
-/-
0.05
0.05
0.50
0.45
10
COOHcis* + *  CO* + OH*
- / -0.07
1.41
1.30
1.48
1.33
11
COOHcis* + H*  CO* + H2O*
-0.04 / -0.04
-0.39
-0.33
0.59
0.55
12
HCO* + *  CO* + H*
- / 0.04
0.23
0.07
0.77
0.59
13
OH* + H*  H2O* + *
-0.03 / -
-1.80
-1.64
0.26
0.26
14
2H*  H2 + 2*
0.01 / -
-0.49
-0.49
0.59
0.57
15
CO2*  CO2 + *
-/-
0.05
0.02
16
H2O*  H2O + *
-/-
0.16
0.10
17
CO*  CO + *
-/-
0.26
0.21
All adsorption and desorption steps are found to be non-activated, and are assumed to be quasi-equilibrated.
‘-’ denotes the presence of only one adsorbate in the initial/final state, and hence the absence of any adsorbateadsorbate interactions
5
Table S.6 PW91 reaction energies (∆E), activation energy barriers (EA) for the elementary steps considered in
the HCOOH decomposition reaction network on Au(100), with (w) and without (w/o) ZPE corrections. All
the values are relative to the infinite separation of species in the initial/final states.
Adsorbate
#
Reaction
∆E / eV
EA / eV
Interaction / eV
W/O
W
W/O
W
IS / FS
ZPE
ZPE
ZPE
ZPE
1
HCOOH + *  HCOOH*
-/-
-0.22
-0.16
2
HCOOH*  HCOOHpa*
-/-
0.29
0.29
0.65
0.59
3
HCOOH* + 2*  HCOO** + H*
- / 0.01
0.56
0.42
1.09
0.87
4
HCOOHpa* + *  COOH* + H*
- / -0.01
0.56
0.44
1.02
0.83
5
HCOOH* + *  HCO* + OH*
- / -0.22
1.64
1.57
2.00
1.91
6
HCOO**  CO2* + H*
- / 0.00
-0.06
-0.17
1.02
0.84
7
HCOO** + H*  H2 + CO2* + 2*
0.01 / -
-0.19
-0.34
1.29
1.11
8
COOH* + *  CO2* + H*
- / 0.00
-0.34
-0.48
0.90
0.68
9
COOH*  COOHcis*
-/-
0.01
0.00
0.58
0.52
10
COOHcis* + *  CO* + OH*
- / -0.04
0.62
0.55
0.78
0.70
11
COOHcis* + H*  CO* + H2O*
-0.01 / -0.05
-0.41
-0.36
0.77
0.68
12
HCO* + *  CO* + H*
- / -0.01
-0.16
-0.29
0.40
0.24
13
OH* + H*  H2O* + *
-0.02 / -
-1.03
-0.92
0.45
0.38
14
2H*  H2 + 2*
-0.03 / -
-0.13
-0.17
0.53
0.47
15
CO2*  CO2 + *
-/-
0.05
0.02
16
H2O*  H2O + *
-/-
0.20
0.14
17
CO*  CO + *
-/-
0.68
0.62
All adsorption and desorption steps are found to be non-activated, and are assumed to be quasi-equilibrated.
‘-’ denotes the presence of only one adsorbate in the initial/final state, and hence the absence of any adsorbateadsorbate interactions
6
Table S.7 PW91 reaction energies (∆E), activation energy barriers (EA) for the elementary steps considered in
the HCOOH decomposition reaction network on Au(211), with (w) and without (w/o) ZPE corrections. All
the values are relative to the infinite separation of species in the initial/final states.
Adsorbate
#
Reaction
∆E / eV
EA / eV
Interaction/eV
W/O
W
W/O
W
IS / FS
ZPE
ZPE
ZPE
ZPE
1
HCOOH + *  HCOOH*
-/-
-0.28
-0.21
2
HCOOH*  HCOOHpa*
-/-
0.31
0.26
0.68
0.63
3
HCOOH* + 2*  HCOO** + H*
- / 0.20
0.40
0.26
1.20
0.98
4
HCOOHpa* + *  COOH* + H*
- / 0.02
0.49
0.37
1.06
0.87
5
HCOOH* + *  HCO* + OH*
- / -0.03
1.47
1.38
1.85
1.74
6
HCOO**  CO2* + H*
- / 0.00
0.04
-0.08
1.03
0.85
7
HCOO** + H*  H2 + CO2* + 2*
0.20 / 0.00
0.02
-0.15
1.39
1.30
8
COOH* + *  CO2* + H*
- / 0.00
-0.31
-0.46
0.96
0.74
9
COOH*  COOHcis*
-/-
0.00
-0.01
0.50
0.44
10
COOHcis* + *  CO* + OH*
- / 0.15
0.58
0.51
1.10
1.00
11
COOHcis* + H*  CO* + H2O*
0.02 / 0.02
-0.34
-0.30
0.95
0.87
12
HCO* + *  CO* + H*
- / 0.02
-0.14
-0.26
0.43
0.28
13
OH* + H*  H2O* + *
0.08 / -
-0.92
-0.81
0.69
0.61
14
2H*  H2 + 2*
-0.02 / -
-0.02
-0.07
0.55
0.49
15
CO2*  CO2 + *
-/-
0.06
0.05
16
H2O*  H2O + *
-/-
0.25
0.20
17
CO*  CO + *
-/-
0.73
0.67
All adsorption and desorption steps are found to be non-activated, and are assumed to be quasi-equilibrated.
‘-’ denotes the presence of only one adsorbate in the initial/final state, and hence the absence of any adsorbateadsorbate interactions
7