Supporting information for

Adsorption characteristics of glycols on

calcite and hematite
Richard Olsen∗, Kim Nes Leirvik, and Bjørn Kvamme

Department of Physics and Technology, University of Bergen,

Allégaten 55, 5007 Bergen, Norway

June 5, 2018

1 More simulation details

All systems were simulated at 298.15 K, where temperature was controlled using the Nosé-
Hoover thermostat 1 with a relaxation time of 100 times a single time step. Electrostatic in-
teractions across periodic boundaries were handled using the P3 M Ewald summation method,
where systems were divided into 32 × 32 × 64 grid points, with fourth order interpolation
between the grid points and a 10 Å cutoff radii.
Initially all particle velocities were assigned randomly from a Gaussian distribution with a
vanishing mean value and standard deviation v, where v is the solution to mv 2 = kB T (where
kB is the Boltzmann constant). Subsequently, the average momentum was subtracted from
each particle to achieve a vanishing total momentum. Systems were first equilibrated in the
NVT ensemble and in the NPT ensemble at 1 atm, where pressure was controlled using the
Martyna-Tobias-Klein algorithm 2 with a barostat relaxation time of 1000 times a single time
step.
All production runs were performed in the NPT ensemble at 298.15 K and 1 atm, using the
same relaxation times as during equilibration. Free energy profiles were calculated for the dif-
ferent glycols, at infinite dilution, by steering single glycol molecules using the ABF algorithm,
with 1 fs time step for 80 ns (i.e., only a single glycol was present in each simulation). Forces
were averaged into 900 bins in 9 Å regions outside the surfaces. The first 8 Å of the region was
divided into four windows of 2 Å, where each window was simulated for 10 ns. To achieve
a better sampling, overlapping windows were applied. Thus, also the last 8 Å of the 9 Å re-
gion was divided into four 2 Å windows, hence resulting in a total of eight windows of 10 ns
for each of the six systems involved. Within each window a value Nfs = 600 was applied (see
Free Energy Calculations within the article) to assure a proper average for the biasing force
calculations. The window force constant was set to 750 kJ/mol for all systems involving cal-
cite. However, for the MEG–hematite and DEG–hematite systems, a force of 2000 kJ/mol was
applied within the two windows closest to the surface, while 750 kJ/mol was applied within
the remaining windows. For the TEG–hematite system, the force applied within the remain-
ing windows was set to 1000 kJ/mol to accommodate the larger forces needed to move the
heavier TEG molecule through the liquid.
∗
Corresponding author: E-mail: richard.olsen@ift.uib.no
2

5 10 Hematite
Calcite
0
0 -10
DG @kJmolD

DG @kJmolD
-20
-5 -30
-40
-10 -50
MEG MEG
DEG -60 DEG
-15 -70
TEG TEG
-80
0 2 4 6 8 10 12 0 2 4 6 8 10 12
z @Å D z @Å D

Figure S1: Comparison between free energy profiles of MEG, DEG and TEG in vicinity of
calcite (left) and hematite (right) in pure water. In the case of calcite z = 0 is positioned
approximately at the surface calcium atoms, while in the case of hematite z = 0 is placed
approximately at the surface iron atoms.

To study glycol adsorption sites on calcite and hematite, as well as glycol dipole moments
in vicinity of the surfaces, simulations with 50% glycol–water mixtures were run in the NPT
ensemble at 298.15 K and 1 atm, using the same relaxation times as for the ABF simulations
described above. Each of the six simulations was run for 10 ns (after equilibration) with a time
step of 1 fs. Simulation parameters were otherwise the same as for the ABF simulations.
To keep simulations from drifting away from initial center of mass coordinates, the center
of mass was updated every 100 time steps during the simulations.

2 Free energy profiles with altered reference point

Figure S1 shows the same free energy profiles as was shown in the article. However, in Fig-
ure S1, the zero energy reference has been defined to be approximately the free energy value
found in the bulk phase of the studied system. This is also a commonly applied energy refer-
ence. Thus, we have included plots that utilize it here for convenience.

3 Force field parameters

The naming convention used for atoms of the molecules is shown in Figure S2, while the
utilized force field parameters are listed in Tables S1, S2, S3, S4 and S5.

Atom i Atom j Type Parameters Comments

Ow Ow LJ 12-6 =0.426768, σ=3.188, α=1 Ref. 3
Ow Hw1 LJ 12-6 =0, σ=0, α=1 Ref. 3
Ow Hw2 LJ 12-6 =0, σ=0, α=1 Ref. 3
Hw1 Hw1 LJ 12-6 =0, σ=0, α=1 Ref. 3
Hw1 Hw2 LJ 12-6 =0, σ=0, α=1 Ref. 3
Hw2 Hw2 LJ 12-6 =0, σ=0, α=1 Ref. 3
Ow HG LJ 12-6 =0, σ=0, α=1 Geom. mix.
Ow OG LJ 12-6 =0.550847, σ=3.12844, α=1 Geom. mix.
Ow CT1 LJ 12-6 =0.343203, σ=3.34036, α=1 Geom. mix.
Ow CT2 LJ 12-6 =0.343203, σ=3.34036, α=1 Geom. mix.
Ow HC1 LJ 12-6 =0.23189, σ=2.82312, α=1 Geom. mix.
Ow HC2 LJ 12-6 =0.23189, σ=2.82312, α=1 Geom. mix.
3. FORCE FIELD PARAMETERS 3

Ow OS LJ 12-6 =0.500086, σ=3.04059, α=1 Geom. mix.

Hw1 HG LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 OG LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 CT1 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 CT2 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 HC1 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 HC2 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw1 OS LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 HG LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 OG LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 CT1 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 CT2 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 HC1 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 HC2 LJ 12-6 =0, σ=0, α=1 Geom. mix.
Hw2 OS LJ 12-6 =0, σ=0, α=1 Geom. mix.
Cac Ow LJ 12-6 =1.12994, σ=2.76049, α=1 Ref. 4
Cc Ow LJ 12-6 =0.486129, σ=3.46922, α=1 Ref. 4
Oc Ow LJ 12-6 =0.611413, σ=3.11864, α=1 Ref. 4
Oc Hw1 LJ 12-6 =2.91737e-05, σ=4.49689, α=1 Ref. 4
Oc Hw2 LJ 12-6 =2.91737e-05, σ=4.49689, α=1 Ref. 4
Or Ow LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 5, 6
Fer Ow LJ 12-8 =105.658, σ=0.998846, α=1 Ref. 5, 6
Fer Ow Buck A=152358, ρ=0.2682, B=695.659 Ref. 5, 6
Ors Ow LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 5, 6
OrsB Ow LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 5, 6
Fes Ow LJ 12-8 =105.658, σ=0.998846, α=1 Ref. 5, 6
Fes Ow Buck A=152358, ρ=0.2682, B=695.659 Ref. 5, 6
FesB Ow LJ 12-8 =105.658, σ=0.998846, α=1 Ref. 5, 6
FesB Ow Buck A=152358, ρ=0.2682, B=695.659 Ref. 5, 6
Orh Ow LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 5, 6
HG HG LJ 12-6 =0, σ=0, α=1 OPLS
HG OG LJ 12-6 =0, σ=0, α=1 OPLS
HG CT1 LJ 12-6 =0, σ=0, α=1 OPLS
HG HC1 LJ 12-6 =0, σ=0, α=1 OPLS
HG CT2 LJ 12-6 =0, σ=0, α=1 OPLS
HG HC2 LJ 12-6 =0, σ=0, α=1 OPLS
HG OS LJ 12-6 =0, σ=0, α=1 OPLS
OG OG LJ 12-6 =0.711, σ=3.07, α=1 OPLS
OG CT1 LJ 12-6 =0.442985, σ=3.27796, α=1 OPLS
OG HC1 LJ 12-6 =0.299309, σ=2.77038, α=1 OPLS
OG CT2 LJ 12-6 =0.442985, σ=3.27796, α=1 OPLS
OG HC2 LJ 12-6 =0.299309, σ=2.77038, α=1 OPLS
OG OS LJ 12-6 =0.645481, σ=2.98379, α=1 OPLS
CT1 CT1 LJ 12-6 =0.276, σ=3.5, α=1 OPLS
CT1 HC1 LJ 12-6 =0.186483, σ=2.95804, α=1 OPLS
CT1 CT2 LJ 12-6 =0.276, σ=3.5, α=1 OPLS
CT1 HC2 LJ 12-6 =0.186483, σ=2.95804, α=1 OPLS
CT1 OS LJ 12-6 =0.402164, σ=3.18591, α=1 OPLS
HC1 HC1 LJ 12-6 =0.126, σ=2.5, α=1 OPLS
HC1 CT2 LJ 12-6 =0.186483, σ=2.95804, α=1 OPLS
HC1 HC2 LJ 12-6 =0.126, σ=2.5, α=1 OPLS
4

HC1 OS LJ 12-6 =0.271728, σ=2.69258, α=1 OPLS

CT2 CT2 LJ 12-6 =0.276, σ=3.5, α=1 OPLS
CT2 HC2 LJ 12-6 =0.186483, σ=2.95804, α=1 OPLS
CT2 OS LJ 12-6 =0.402164, σ=3.18591, α=1 OPLS
HC2 HC2 LJ 12-6 =0.126, σ=2.5, α=1 OPLS
HC2 OS LJ 12-6 =0.271728, σ=2.69258, α=1 OPLS
OS OS LJ 12-6 =0.586, σ=2.9, α=1 OPLS
HG Cac LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG Cc LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG Oc LJ 12-6 =0, σ=0, α=1 Geom. mix.
OG Cac LJ 12-6 =1.1926, σ=2.69771, α=1 Geom. mix.
OG Cc LJ 12-6 =0.512182, σ=3.42603, α=1 Geom. mix.
OG Oc LJ 12-6 =0.643301, σ=3.08041, α=1 Geom. mix.
CT1 Cac LJ 12-6 =0.743041, σ=2.88045, α=1 Geom. mix.
CT1 Cc LJ 12-6 =0.319113, σ=3.6581, α=1 Geom. mix.
CT1 Oc LJ 12-6 =0.400806, σ=3.28907, α=1 Geom. mix.
HC1 Cac LJ 12-6 =0.502046, σ=2.43442, α=1 Geom. mix.
HC1 Cc LJ 12-6 =0.215613, σ=3.09166, α=1 Geom. mix.
HC1 Oc LJ 12-6 =0.27081, σ=2.77978, α=1 Geom. mix.
CT2 Cac LJ 12-6 =0.743041, σ=2.88045, α=1 Geom. mix.
CT2 Cc LJ 12-6 =0.319113, σ=3.6581, α=1 Geom. mix.
CT2 Oc LJ 12-6 =0.400806, σ=3.28907, α=1 Geom. mix.
HC2 Cac LJ 12-6 =0.502046, σ=2.43442, α=1 Geom. mix.
HC2 Cc LJ 12-6 =0.215613, σ=3.09166, α=1 Geom. mix.
HC2 Oc LJ 12-6 =0.27081, σ=2.77978, α=1 Geom. mix.
OS Cac LJ 12-6 =1.0827, σ=2.62196, α=1 Geom. mix.
OS Cc LJ 12-6 =0.464984, σ=3.32982, α=1 Geom. mix.
OS Oc LJ 12-6 =0.584021, σ=2.99391, α=1 Geom. mix.
HG Fer LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG Fes LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG FesB LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG Or LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG Ors LJ 12-6 =0, σ=0, α=1 Geom. mix.
HG OrsB LJ 12-6 =0, σ=0, α=1 Geom. mix.
OG Fer LJ 12-6 =0.00518193, σ=3.53578, α=1 Geom. mix.
OG Fes LJ 12-6 =0.00518193, σ=3.53578, α=1 Geom. mix.
OG FesB LJ 12-6 =0.00518193, σ=3.53578, α=1 Geom. mix.
OG Or LJ 12-6 =0.679919, σ=3.1174, α=1 Geom. mix.
OG Ors LJ 12-6 =0.679919, σ=3.1174, α=1 Geom. mix.
OG OrsB LJ 12-6 =0.679919, σ=3.1174, α=1 Geom. mix.
CT1 Fer LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT1 Fes LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT1 FesB LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT1 Or LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
CT1 Ors LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
CT1 OrsB LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
HC1 Fer LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC1 Fes LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC1 FesB LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC1 Or LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
HC1 Ors LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
3. FORCE FIELD PARAMETERS 5

HC1 OrsB LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.

CT2 Fer LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT2 Fes LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT2 FesB LJ 12-6 =0.00322858, σ=3.77528, α=1 Geom. mix.
CT2 Or LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
CT2 Ors LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
CT2 OrsB LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
HC2 Fer LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC2 Fes LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC2 FesB LJ 12-6 =0.00218143, σ=3.1907, α=1 Geom. mix.
HC2 Or LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
HC2 Ors LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
HC2 OrsB LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
OS Fer LJ 12-6 =0.00470441, σ=3.43649, α=1 Geom. mix.
OS Fes LJ 12-6 =0.00470441, σ=3.43649, α=1 Geom. mix.
OS FesB LJ 12-6 =0.00470441, σ=3.43649, α=1 Geom. mix.
OS Or LJ 12-6 =0.617264, σ=3.02986, α=1 Geom. mix.
OS Ors LJ 12-6 =0.617264, σ=3.02986, α=1 Geom. mix.
OS OrsB LJ 12-6 =0.617264, σ=3.02986, α=1 Geom. mix.
HG Orh LJ 12-6 =0, σ=0, α=1 Geom. mix.
OG Orh LJ 12-6 =0.679919, σ=3.1174, α=1 Geom. mix.
CT1 Orh LJ 12-6 =0.42362, σ=3.32857, α=1 Geom. mix.
HC1 Orh LJ 12-6 =0.286225, σ=2.81316, α=1 Geom. mix.
Cac Oc LJ 12-6 =162254, σ=1, α=0 Ref. 4, Optimized
Cc Cc LJ 12-6 =0.726658, σ=4.12407, α=1 Ref. 4, Optimized
Cc Oc LJ 12-6 =226.005, σ=1, α=0 Ref. 4, Optimized
Oc Oc LJ 12-6 =106765, σ=1, α=0 Ref. 4, Optimized
Fer Fer LJ 12-6 =3.77671e-05, σ=4.07222, α=1 Ref. 6
Fer Fes LJ 12-6 =3.77671e-05, σ=4.07222, α=1 Ref. 6
Fer FesB LJ 12-6 =3.77671e-05, σ=4.07222, α=1 Ref. 6
Fer Or LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Fer Ors LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Fer OrsB LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Fes Fes LJ 12-6 =3.77671e-05, σ=4.07222, α=1 Ref. 6
FesB FesB LJ 12-6 =3.77671e-05, σ=4.07222, α=1 Ref. 6
Fes Or LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
FesB Or LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Fes Ors LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
FesB OrsB LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Or Or LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Or Ors LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Or OrsB LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Ors Ors LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
OrsB OrsB LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Fer Orh LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Fes Orh LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
FesB Orh LJ 12-6 =0.00495636, σ=3.61883, α=1 Ref. 6
Or Orh LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Ors Orh LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
OrsB Orh LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
Orh Orh LJ 12-6 =0.650196, σ=3.16554, α=1 Ref. 6
6

∗ Energy unit is kJ/mol and distance unit is Å.

Table S1: Force Field Parameters of Non-Bonded Interactions.

Atom i Atom j Type Parameters Comments

Ow Hw1 Harm K r =1882.8, r0 =0.9572 Ref. 7–9
Ow Hw2 Harm K r =1882.8, r0 =0.9572 Ref. 7–9
HG OG Harm K r =2313.75, r0 =0.945 OPLS
HC1 CT1 Harm K r =1422.56, r0 =1.09 OPLS
HC2 CT2 Harm K r =1422.56, r0 =1.09 OPLS
CT1 OG Harm K r =1338.88, r0 =1.41 OPLS
CT1 CT2 Harm K r =1121.31, r0 =1.529 OPLS
CT2 OS Harm K r =1338.88, r0 =1.41 OPLS
CT2 CT2 Harm K r =1121.31, r0 =1.529 OPLS
CT1 CT1 Harm K r =1121.31, r0 =1.529 OPLS
Hrh Orh Harm K r =2318.5, r0 =1 Ref. 10
∗ Energy unit is kJ/mol and distance unit is Å.

Table S2: Bond Parameters.

Atom i Atom j Atom k Type Parameters Comments

Hw1 Ow Hw2 Harm K θ =230.12, θ0 =104.52 Ref. 7–9
HG OG CT1 Harm K θ =230.12, θ0 =108.5 OPLS
HC1 CT1 OG Harm K θ =146.44, θ0 =109.5 OPLS
HC1 CT1 HC1 Harm K θ =138.072, θ0 =107.8 OPLS
HC1 CT1 CT2 Harm K θ =156.9, θ0 =110.7 OPLS
HC2 CT2 CT1 Harm K θ =156.9, θ0 =110.7 OPLS
HC2 CT2 HC2 Harm K θ =138.072, θ0 =107.8 OPLS
HC2 CT2 OS Harm K θ =146.44, θ0 =109.5 OPLS
HC2 CT2 CT2 Harm K θ =156.9, θ0 =110.7 OPLS
CT1 CT2 OS Harm K θ =209.2, θ0 =109.5 OPLS
CT2 CT1 OG Harm K θ =209.2, θ0 =109.5 OPLS
CT2 OS CT2 Harm K θ =251.04, θ0 =109.5 OPLS
CT2 CT2 OS Harm K θ =209.2, θ0 =109.5 OPLS
HC1 CT1 CT1 Harm K θ =156.9, θ0 =110.7 OPLS
CT1 CT1 OG Harm K θ =209.2, θ0 =109.5 OPLS
Oc Cc Oc Harm K θ =926, θ0 =120 Ref. 4
FesB Orh Hrh Harm K θ =152.52, θ0 =109.47 Ref. 10
∗ Energy unit is kJ/mol and angle unit is degree.

Table S3: Angle Parameters.

Atom i Atom j Atom k Atom l Type Parameters Comments

HG OG CT1 HC1 OPLS V1 =0, V2 =0, V3 =1.4744 OPLS
HG OG CT1 CT2 OPLS V1 =-1.4895, V2 =-0.728,
V3 =2.0585 OPLS
HC1 CT1 CT2 HC2 OPLS V1 =0, V2 =0, V3 =1.2552 OPLS
HC1 CT1 CT2 OS OPLS V1 =0, V2 =0, V3 =1.9581 OPLS
REFERENCES 7

HC2 CT2 CT1 OG OPLS V1 =0, V2 =0, V3 =1.9581 OPLS

HC2 CT2 OS CT2 OPLS V1 =0, V2 =0, V3 =3.1798 OPLS
HC2 CT2 CT2 HC2 OPLS V1 =0, V2 =0, V3 =1.2552 OPLS
HC2 CT2 CT2 OS OPLS V1 =0, V2 =0, V3 =1.9581 OPLS
CT1 CT2 OS CT2 OPLS V1 =2.7196, V2 =-1.046,
V3 =2.8033 OPLS
CT2 OS CT2 CT2 OPLS V1 =2.7196, V2 =-1.046,
V3 =2.8033 OPLS
OG CT1 CT2 OS OPLS V1 =18.0707, V2 =0, V3 =0 OPLS
OS CT2 CT2 OS OPLS V1 =-2.3012, V2 =-0, V3 =0 OPLS
HG OG CT1 CT1 OPLS V1 =-1.4895, V2 =-0.728,
V3 =2.0585 OPLS
HC1 CT1 CT1 HC1 OPLS V1 =0, V2 =0, V3 =1.2552 OPLS
HC1 CT1 CT1 OG OPLS V1 =0, V2 =0, V3 =1.9581 OPLS
OG CT1 CT1 OG OPLS V1 =39.7815, V2 =0, V3 =0 OPLS
Oc Cc Oc Oc Harm K φ,h =28.9, d=-1, n=2 Ref. 4
∗ Energyunit is kJ/mol. For harmonic potentials U = K φ,h [1 + d cos(nφ)]. For OPLS type
dihedrals V4 =0.

Table S4: Dihedral Parameters.

Atom Q Atom Q Atom Q

Oc -0.88900000 Cc 0.99900000 Cac 1.66800000
HG 0.43500000 OG -0.70000000 CT1 0.14500000
HC1 0.06000000 CT2 0.14000000 HC2 0.03000000
OS -0.40000000 Ow -0.83000000 Hw1 0.41500000
Hw2 0.41500000 OrsB -0.96920212 Or -1.05000000
FesB 1.63408345 Fer 1.57500000 Ors -1.05000000
Fes 1.57500000

Table S5: Partial Charges Assigned to Each Atom Type.

References
[1] Nosé, S. A molecular dynamics method for simulations in the canonical ensemble. Mol.
Phys. 1984, 52, 255–268.
[2] Martyna, G. J.; Tobias, D. J.; Klein, M. L. Constant pressure molecular dynamics algo-
rithms. J. Chem. Phys. 1994, 101, 4177–4189.
[3] Price, D. J.; Brooks, C. L. A modified TIP3P water potential for simulation with Ewald
summation. J. Chem. Phys. 2004, 121, 10096–10103.
[4] Xiao, S.; Edwards, S. A.; Gräter, F. A new transferable forcefield for simulating the me-
chanics of CaCO3 crystals. J. Phys. Chem. C 2011, 115, 20067–20075.
[5] Curtiss, L. A.; Halley, J. W.; Hautman, J.; Rahman, A. Nonadditivity of ab initio pair
potentials for molecular dynamics of multivalent transition metal ions in water. J. Chem.
Phys. 1987, 86, 2319–2327.
[6] Kerisit, S. Water structure at hematite–water interfaces. Geochim. Cosmochim. Acta 2011,
75, 2043–2061.
8 REFERENCES

[7] Brooks, B. R.; Bruccoleri, R. E.; Olafson, B. D.; States, D. J.; Swaminathan, S.; Karplus, M.
CHARMM: A program for macromolecular energy, minimization, and dynamics calcula-
tions. J. Comput. Chem. 1983, 4, 187–217.

[8] Field, M. J.; Bash, P. A.; Karplus, M. A combined quantum mechanical and molecular
mechanical potential for molecular dynamics simulations. J. Comput. Chem. 1990, 11,
700–733.

[9] MacKerell, A. D. et al. All-atom empirical potential for molecular modeling and dynamics
studies of proteins. J. Phys. Chem. B 1998, 102, 3586–3616.

[10] Cygan, R. T.; Liang, J.-J.; Kalinichev, A. G. Molecular models of hydroxide, oxyhydroxide,
and clay phases and the development of a general force field. J. Phys. Chem. B 2004, 108,
1255–1266.

Calcium carbonate Iron oxide

Oc Fes
Cac Ors
Or

Cc Fe
(Fes: Outermost iron of rust, Ors: Outermost oxgen of rust)

Water Diethylene glycol Ethylene glycol

HC2
HC2 HC2 HC2 OG HG
HC1 CT2 HG
Ow CT2 OG
CT1 HC1 CT1
HC1 OS HC1 CT1
CT1 HC1 HC1
Hw1 Hw2 OG HC1
OG HC1
HG
HG
Triethylene glycol HydroxylaIon of hemaIte
HC2 FesB
HC1 2 HC2
CT1 CT OS HG Hrh
HG HC2 CT2 HC1
OS OG Orh
OG HC2 CT2 CT1
HC1 HC2 CT2 HC2
HC1 OrsB
HC2 HC2

(FesB, OrsB: Charge balanced outermost iron and outermost oxygen of rust)

Figure S2: Naming convention used for atoms of the molecules.

Hydronium Bicarbonate
Hhy