Supplementary information

“On the mechanism of methanol synthesis

on Cu through CO2 hydrogenation”
Lars C. Grabow and Manos Mavrikakis

Gas phase corrections to PW91-GGA energies

It is well known that DFT-GGA, including PW91 calculations often show large
deviations from handbook values for gas phase species. In the present case, for instance,
we see absolute errors of up to 71 kJ/mol (for ∆H of HCOOH → CO + H2O at 500 K, see
Table 1). On the other hand, entropy changes show absolute errors of less than 13
J/mol/K (relative errors < ~10%). For the reaction network studied, we found that we can
attribute the main source of DFT errors to the enthalpies of CO and HCOOH. By
adjusting only the enthalpies of CO and HCOOH in the gas phase by -0.6, and +0.2 eV,
respectively, we were able to reproduce handbook values for all considered overall gas
phase reactions with absolute errors of less than 10 kJ/mol (Table 1).

Table 1: Enthalpy and entropy changes for several gas phase reactions related to MeOH synthesis at
T = 500 K. The error in the DFT values can be almost entirely attributed to the enthalpies of CO and
HCOOH. For the microkinetic model CO(gas) was stabilized by 0.6 eV, HCOOH(gas) destabilized by
0.2 eV, resulting in the corrected DFT values ∆Hcorrected that are in reasonable agreement with
handbook values.1 The affected reaction enthalpies are highlighted in bold.
Reaction Handbook DFT
∆H ∆S ∆H ∆Hcorrected ∆S
[kJ/mol] [J/mol/K] [kJ/mol] [kJ/mol] [J/mol/K]
CO2 + 3H2 → CH3OH + H2O -57.86 -198.78 -62.00 -62.00 -209.98
CO + 2H2 → CH3OH -97.56 -237.22 -160.00 -102.00 -244.31
CO2 + H2 → CO + H2O 39.70 38.44 98.00 40.00 34.33
CO2 + H2 → HCOOH 11.63 -96.74 -1.00 19.00 -108.93
CO2 + 2H2 → CH2O + H2O 37.79 -80.89 44.00 44.00 -93.42
CH2O + H2 → CH3OH -95.65 -117.89 -106.00 -106.00 -116.56
HCOOH → CO + H2O 28.07 135.18 99.00 21.00 143.26

Entropy prediction from DFT

For gas phase species the entropy contributions of free translational and rotational
modes is well defined and depend on the mass, moment of inertia and the rotational
symmetry of the molecule.2 The vibrational entropy contributions can be calculated using
the harmonic normal mode approximation:3

S1
 # of modes
 xi 
Svib = ∑ i
 xi
 e −1
− ln 1 − e − xi 

( )
(1)
hν
xi = i
k BT

This procedure usually predicts gas phase entropies within a few percent of
handbook values; an indicative graphical comparison for methanol and formaldehyde is
given in Figure 1.

Methanol (CH3OH) Formaldehyde (CH2 O)

120 380 75 300

Cp Yaw's Handbook Cp NIST
360 70 290
100 Cp DFT Cp DFT
Entropy Yaw's Handbook 340 65 Entropy NIST 280
Entropy DFT 270

Cp in J/mol/K
Cp in J/mol/K

Entropy DFT

Entropy in J/mol/K
Entropy in J/mol/K
80 320 60
260
300 55
60 250
280 50
240
40 260 45
230
Max. relative error 240 40 Max. relative error 220
20 Cp = 15.88 % Cp = 0.69 %
220 35 210
S = 3.49 % S = 0.05 %
0 200 30 200
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
T in K T in K

Figure 1 Comparison of DFT-calculated entropy and heat capacity values with respective handbook
values for methanol1 (left) and formaldehyde4 (right).

For adsorbed species the vibrational entropy contribution can be obtained exactly
as in the case of gas phase species, but the translational and rotational modes become
frustrated and need to be treated differently. We defined two translational modes within
the surface plane and separated these translational modes before diagonalizing the
Hessian matrix.5 For the entropy calculation we treated the frustrated translational and
rotational modes identical to vibrational modes.3 The extent of frustration for a
translational mode is related to the mobility of a species on the surface. Since the
translational entropy cannot exceed the entropy of a 2D gas (complete mobility on the
surface) we used this value as an upper bound for translational entropy contributions.
Because of the lack of detailed experimental data, we could not verify that this procedure
works equally well for adsorbed species, but based on the high quality of the results for
the gas phase species, we are confident in assuming that the errors involved are
acceptable.

S2
Parameterization of the Shomate equation from DFT results
The temperature dependence of entropy and enthalpy of all species involved was
described using the Shomate equation according to NIST.4

t = T [ K ] /1000
C p [ J / mol ⋅ K ] = A + Bt + Ct 2 + Dt 3 + E / t
(2)
H − H T 0 [kJ / mol ] = At + Bt 2 / 2 + Ct 3 / 3 + Dt 4 / 4 − E / t + F − H
S[ J / mol ⋅ K ] = A ln(t ) + Bt + Ct 2 / 2 + Dt 3 / 3 − E /(2t 2 ) + G

In order to find the necessary parameters we used the following procedure:

1. We used the vibrational information obtained from DFT calculations to

predict entropies between 10 and 300 K and fit the Shomate parameters
A, B, C, D, E, and G. The parameter H was arbitrarily set to the
reference enthalpy H T 0 and F was determined at the reference state

using T0 = 10 K and H10 K = U0 + ZPE (U0 = electronic energy, ZPE =

# of modes
zero point energy = ∑ i
hν i ). The reference temperature of 10 K

was chosen, because T = 0 K results in an undefined value during the

evaluation of Cp, since the temperature appears in the denominator.

2. Using the Shomate parameters from step 1, we find the standard state
298.15K
enthalpy at T = 298.15 K as H 298.15 K = U 0 + ZPE + ∫
10K
C p (T )dT .

3. We repeat step 1 to find the Shomate parameters in the temperature

range between 300 – 1200 K and use T0 = 298.15 K with H298.15 K from
step 2.

This procedure was applied to all species (gas phase species, adsorbed species, and
transition states) and the resulting parameters for T = 300-1200 K are given in Table 2-4.

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Table 2 Shomate parameters for gas phase species.
Species ∆H0 [kJ/mol] S0 [J/mol/K] A B C D E F G H
H2 -3032.90 134.66 29.91936 -2.35028 1.54743 0.57934 -0.02578 -3041.82 171.35 -3032.90
CO -57015.02 202.05 27.01916 0.39882 10.80028 -5.39747 0.11318 -57022.80 234.83 -57015.02
CO2 -99310.40 218.57 27.72336 48.60556 -28.93575 6.74397 -0.18280 -99321.19 237.82 -99310.40
H2O -45229.41 189.11 28.05552 14.46211 -2.99413 1.07386 0.12203 -45237.98 219.56 -45229.41
CH2O -60097.98 218.88 3.04758 101.92105 -56.26415 12.54532 0.62240 -60100.85 198.06 -60097.98
HCOOH -102344.61 251.48 15.84489 143.98941 -105.96425 31.14424 -0.14154 -102355.33 231.37 -102344.61
CH3OH -63234.62 241.84 10.49452 153.59317 -92.85784 24.06304 0.19502 -63243.14 213.77 -63234.62
HCOOCH3 -120355.88 290.69 0.11567 266.94426 -176.86514 47.09685 0.38750 -120365.01 220.88 -120355.88

Table 3 Shomate parameters for surface species.

Species ∆H0 [kJ/mol] S0 [J/mol/K] A B C D E F G H
H* -1531.30 1.73 11.33569 12.63472 5.60683 -6.93690 -0.91838 -1538.85281 6.38 -1531.80
O* -42119.61 13.85 18.66427 18.08991 -19.15144 7.00167 -0.29627 -42128.91229 30.16 -42121.71
OH* -43709.42 30.79 31.16300 30.48403 -33.39338 13.81303 -0.28834 -43724.94675 59.14 -43713.60
H2O* -45242.45 72.60 31.50218 55.98915 -49.17565 18.64340 0.21065 -45253.22508 97.21 -45242.45
CO* -57095.38 52.86 26.01212 44.22368 -36.26171 11.65813 0.28361 -57111.39862 74.24 -57102.93
CO2* -99312.37 67.84 34.89269 65.42940 -47.83766 13.94892 -0.12010 -99325.69152 91.88 -99312.37
CO3* -141424.64 71.92 50.45768 93.33982 -69.45108 18.73342 -0.94381 -141446.42048 102.79 -141424.64
HCO3* -143053.16 79.30 32.21331 168.52782 -133.55600 39.90279 -0.45121 -143070.66652 71.09 -143053.16
HCO* -58541.39 57.42 30.46590 63.30430 -39.70797 9.89931 -0.15730 -58562.97355 76.21 -58550.88
COH* -58506.32 63.00 33.92065 66.00744 -52.46305 16.45180 -0.29905 -58519.93577 84.88 -58506.32
HCOH* -60056.27 65.87 35.92435 80.14183 -42.57043 8.66872 -0.46508 -60081.62377 84.67 -60066.15
HCOO* -100862.33 62.31 20.21109 133.71969 -96.20544 26.52968 0.00799 -100882.59268 50.99 -100871.45
H2CO2* -102300.36 70.10 19.60526 171.60968 -124.55110 35.33535 -0.36767 -102322.12536 45.83 -102308.45
COOH* -100781.30 64.81 42.03276 86.90417 -57.97981 14.68080 -0.65200 -100799.40198 88.57 -100781.30
HCOOH* -102357.14 81.62 22.89629 154.92162 -106.80911 29.30562 -0.05589 -102383.95741 67.32 -102370.94
CH2O* -60097.65 60.45 33.94654 78.52549 -39.69646 7.53698 -0.50265 -60122.30973 77.01 -60107.35
CH3O* -61711.37 68.67 9.97873 156.88807 -98.16564 25.16016 0.29932 -61729.37780 39.80 -61721.25
CH2OH* -61619.88 70.30 40.12136 94.75660 -47.33624 9.31632 -0.79088 -61649.94548 88.21 -61631.52
CH3O2* -103865.64 75.54 20.12942 198.83174 -142.56348 40.85552 -0.26263 -103892.52228 45.13 -103877.98
CH3OH* -63247.94 92.76 12.80521 181.34809 -115.33416 30.76361 0.30468 -63257.83803 60.76 -63247.94
HCOOCH3* -120354.12 129.33 9.96557 278.66296 -184.88579 49.11710 0.37995 -120366.66345 68.24 -120354.12
CH2OOCH3* -121875.38 127.40 0.49307 332.64060 -222.49264 59.49041 0.40746 -121887.09554 40.49 -121875.38

S4
Table 4 Shomate parameters for the transition states of all surface elementary steps. Steps R22 and R23 were spontaneous and no Shomate parameters
have been obtained for those transition states.
# Reaction ∆H0 S0
A B C D E F G H
[kJ/mol] [J/mol/K]
R9 CO* + O* → CO2* + * -99155.21 48.72 39.77641 49.79898 -41.81240 13.78403 -0.19116 -99169.58 82.64 -99155.21
R10 CO* + OH* → COOH* + * -100751.01 57.85 49.24171 64.06684 -51.83247 17.40026 -0.51591 -100769.85 97.57 -100751.01
R11 COOH* + * → CO2* + H* -100684.63 71.50 43.86315 86.00022 -61.74360 16.22321 -0.51069 -100702.73 98.68 -100684.63
R12 COOH* + OH* → CO2* + H2O* -144534.31 86.52 41.43755 177.08407 -136.23036 39.69581 -0.44491 -144554.90 87.08 -144534.31
R13 COOH* + H* → HCOOH* + * -102249.83 82.14 30.29358 154.95668 -121.85889 36.30357 -0.46912 -102266.32 75.07 -102249.83
R14 H2O* + * → OH* + H* -45134.03 36.99 36.52043 48.67768 -42.36234 14.52167 -0.76204 -45149.30 64.15 -45134.03
R15 OH* + * → O* + H* -45134.03 36.99 36.52043 48.67768 -42.36234 14.52167 -0.76204 -45149.30 64.15 -45134.03
R16 2 OH* → H2O* + O* -87369.11 46.40 43.27135 71.29033 -48.98798 13.10773 -0.87096 -87387.70 74.69 -87369.11
R17 CO2* + H* → HCOO* + * -100766.06 80.03 36.20834 92.43362 -60.24713 13.94666 -0.50759 -100782.16 96.01 -100766.06
R18 HCOO* + H* → H2COO* + * -102245.85 74.67 9.23900 202.99259 -160.29134 47.30315 -0.21777 -102257.03 30.83 -102245.85
R19 HCOO* + H* → HCOOH* + * -102313.47 85.05 21.93581 168.46443 -127.01810 36.27011 -0.20790 -102327.15 65.53 -102313.47
R20 HCOOH* + H* → CH3O2* + * -103792.85 117.39 17.73253 212.32738 -162.71098 47.99305 -0.21986 -103806.97 81.13 -103792.85
R21 H2COO* + H* → CH3O2* + * -103767.22 58.58 19.99293 209.90407 -158.65663 46.13506 -0.66242 -103783.42 23.13 -103767.22
R24 CH2O* + H* → CH3O* + * -61610.15 66.81 13.46197 161.65168 -112.77939 30.96093 -0.06010 -61620.61 39.32 -61610.15
R25 CH3O* + H* → CH3OH* -63137.80 72.12 11.14910 192.68449 -128.75674 34.48273 0.06465 -63148.41 33.96 -63137.80
R26 CO* + H* → HCO* + * -58536.16 53.61 29.47559 59.30998 -37.84647 8.91036 0.07370 -58547.02 73.60 -58536.16
R27 CO* + H* → COH* + * -58417.06 55.19 33.02304 64.28161 -48.64128 13.42139 -0.26511 -58430.25 76.55 -58417.06
R28 HCOO* + * → HCO* + O* -100647.73 50.69 44.05217 69.64254 -45.59243 11.87633 -0.60793 -100665.62 81.74 -100647.73
R29 HCO* + H* → HCOH* + * -59993.01 57.92 37.92846 78.86947 -47.85059 10.65860 -0.71472 -60009.82 78.34 -59993.01
R30 HCO* + H* → CH2O* + * -60030.70 54.13 32.47613 78.60609 -39.56617 6.05852 -0.54945 -60045.38 68.64 -60030.70
R31 CH2O* + H* → CH2OH* + * -61557.38 99.73 38.27858 104.00842 -61.20617 14.27018 -0.48535 -61574.53 114.93 -61557.38
R32 HCOH* + H* → CH2OH* + * -61539.89 59.00 21.39795 148.47799 -106.91178 30.53382 -0.28019 -61552.92 43.55 -61539.89
R33 CH2OH* + H* → CH3OH* + * -63105.11 70.04 16.72169 191.63862 -139.78273 40.88611 -0.40516 -63118.81 36.73 -63105.11
R34 HCOOH* + * → HCO* + OH* -102211.93 75.92 52.40376 86.71645 -60.19571 17.87170 -0.69554 -102233.24 112.09 -102211.93
R35 HCOOH* + * → HCOH* + O* -102129.88 56.09 46.83617 87.32609 -48.50304 10.50542 -0.88588 -102150.29 83.85 -102129.88
R36 CH3O2* + * → CH2OH* + O* -100560.44 50.39 47.60863 69.89409 -53.84299 16.39219 -0.66249 -100579.52 85.69 -100560.44
R37 CO2* + O* → CO3* + * -103683.49 89.36 50.54734 109.68038 -63.21037 15.36873 -0.78804 -103705.55 116.10 -103683.49
R38 CO3* + H* → HCO3* + * -141405.82 61.25 48.18408 76.35203 -55.92084 15.52257 -0.60222 -141425.14 95.76 -141405.82
R39 O*+ HCO* → OH*+ CO* -142864.01 77.81 38.64365 164.83304 -137.43158 41.60876 -0.82555 -142884.49 76.55 -142864.01
R40 OH*+ HCO* → H2O*+ CO* -100675.72 52.14 41.44031 76.58622 -44.55860 8.79125 -0.58927 -100693.08 78.06 -100675.72
R41 HCO2* + HCO* → HCOOH*+ CO* -102227.44 87.54 49.51651 99.03895 -66.71706 17.71694 -0.50888 -102247.76 117.89 -102227.44
R42 HCO2*+ HCO* → H2CO2*+ CO* -159358.55 145.10 43.07339 214.09261 -156.30804 43.26146 0.00056 -159379.61 139.97 -159358.55
R43 HCOOH* + HCO* → CH3O2*+ CO* -159337.21 110.53 34.10656 231.28792 -169.41994 46.95892 -0.18889 -159356.89 88.91 -159337.21
R44 CH2O* + HCO* → CH3O*+ CO* -160867.83 114.35 37.00545 252.88709 -181.37550 50.29116 -0.18423 -160889.22 90.33 -160867.83
R45 CH3O*+ HCO* → CH3OH*+ CO* -120223.53 112.10 20.74758 224.10965 -136.70030 33.42479 0.18345 -120253.59 77.21 -120239.20
R46 CH3O* + HCOO* → HCOOCH3* + O* -162454.44 108.47 22.99376 295.33635 -203.85100 55.91858 -0.11775 -162473.12 56.16 -162454.44
R47 CH3O* + CH2O* → H2COOCH3* + * -121803.32 144.23 6.00097 258.70613 -154.77979 37.64905 0.50409 -121827.32 83.75 -121817.02
R48 HCOOCH3* + H* → H2COOCH3* + * -121801.23 115.16 4.48671 331.58455 -231.48193 63.63332 0.21034 -121814.68 32.65 -121801.23
R49 2 CH2O* → HCOOCH3* + * -120092.50 147.43 5.23018 269.27740 -178.63004 46.53647 0.25050 -120103.70 82.42 -120092.50

S5
Transition state weight ω
Within the framework of a microkinetic model, activation energy barriers and
reaction enthalpies cannot be fitted independently since they always have to obey the
thermodynamic constraint that ∆H = E f − E r . Hence, instead of fitting reaction barriers

directly, we introduced a new variable ω that describes the proximity of the transition
state to either the initial or final state of the reaction and varies between 0 and 1. In
particular, a value of ω = 0 corresponds to an initial-state like behavior of the transition
state, whereas ω = 1 describes a final-state like transition state. The forward barrier is
then calculated as

E f = E f , DFT + ω (∆H − ∆EDFT ) (3)

where E f , DFT and ∆E DFT correspond to the activation energy barrier and energy

change derived from DFT and are kept constant throughout. The reaction enthalpy ∆H
depends on the temperature (Cp corrections) and can be altered during the fitting process
by (de-)stabilizing the involved species. Using equation (3) to calculate the activation
energy by varying ω ensures that the fitted barrier remains qualitatively similar to the
predicted barrier from DFT calculations. This idea is analogous to the Brønsted-Evans-
Polanyi principle for surface reactions where activation energies are linearly correlated to
reaction enthalpies across different transition metals.6-8 For initial-state like behavior of
the transition state (ω = 0) the forward barrier of the reaction remains fixed at the DFT
value and the reverse barrier is chosen to be thermodynamically consistent. In the limit of
ω = 1, the reverse barrier is fixed and the forward barrier is adjusted to be
thermodynamically consistent. In the general case where 0 < ω < 1, the difference
between ∆H and ∆E DFT is distributed on the forward and reverse barrier with ω as the

weighting factor. Furthermore, ω is not an arbitrarily adjusted parameter but reflects a

chemical property of the transition state. We estimated its value from NEB calculations
reaction coordinate(transition state)
as the ratio: . Independent of the value of ω we
reaction coordinate(final state)

S6
always enforce that E f ≥ 0 for exothermic reactions and E f ≥ ∆H for endothermic

reactions by limiting the allowable range for E f dynamically in the microkinetic model.

References

(1) Yaws, C. L. Yaws' Handbook of Thermodynamic and Physical Properties

of Chemical Compounds; Knovel, 2003.
(2) Dumesic, J. A.; Rudd, D. F.; Aparicio, L. L.; Rekoske, J. E.; Treviño, A.
A. The Microkinetics of Heterogeneous Catalysis; American Chemical Society:
Washington, DC, 1993.
(3) Gokhale, A. A.; Kandoi, S.; Greeley, J. P.; Mavrikakis, M.; Dumesic, J. A.
Chem. Eng. Sci. 2004, 59, 4679.
(4) In NIST Standard Reference Database Number 69, June 2005 Release;
Mallard, W. G., Ed.; National Institute of Standards and Technology: 2005.
(5) Ochterski, J. W. 1999.
(6) Nørskov, J. K.; Bligaard, T.; Logadottir, A.; Bahn, S.; Hansen, L. B.;
Bollinger, M.; Bengaard, H.; Hammer, B.; Sljivancanin, Z.; Mavrikakis, M.; Xu, Y.;
Dahl, S.; Jacobsen, C. J. H. J. Catal. 2002, 209, 275.
(7) Xu, Y.; Ruban, A. V.; Mavrikakis, M. J. Am. Chem. Soc. 2004, 126, 4717.
(8) Alcala, R.; Mavrikakis, M.; Dumesic, J. A. J. Catal. 2003, 218, 178.

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