ARTICLE

pubs.acs.org/JPCC

Ab Initio, Physically Motivated Force Fields for CO2 Adsorption

in Zeolitic Imidazolate Frameworks
Jesse G. McDaniel,† Kuang Yu,† and J. R. Schmidt*
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin—Madison, Madison, Wisconsin 53706,
United States
bS Supporting Information
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ABSTRACT: We present an entirely ab initio methodology, based on symmetry adapted

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perturbation theory (SAPT), for constructing force-fields to study CO2 adsorption in

nanoporous zeolitic imidazolate frameworks (ZIFs). Our approach utilizes the SAPT energy
decomposition to generate physically motivated force fields for the CO2-ZIF interaction, with
explicit terms representing exchange, electrostatic, induction and dispersion interactions. Each
of these terms is fit to the corresponding term in the SAPT energy decomposition, yielding a
force field entirely free of empirical parameters. This approach was utilized to construct force
fields describing the CO2 interaction with both ZIF-8 and ZIF-71. In conjunction with our
existing CO2
CO2 force field, parametrized in a consistent manner, we validate our force
fields using grand canonical Monte Carlo simulations and obtain good agreement with the
corresponding experimental CO2 adsorption isotherms. Furthermore, the explicit correspon-
dence between force field terms and fundamental interaction types (dispersion, electrostatics,
and induction) allows for an analysis of the underlying physics controlling ZIF gas adsorption
that is far more direct and well-defined than with the generic force fields that had been previously utilized to study these systems.
As our force fields are free from empirical parameters, these results demonstrate the potential for computationally screening novel
ZIFs for flue gas separation applications with near quantitative accuracy.

’ INTRODUCTION interactions between different gas molecules and ZIF frame-

Concern about the increasing production of carbon dioxide
(CO2) and its role in global warming has led to significant in-
terest in postcombustion CO2 capture and separation. As coal
fired power plants are one of the major point-source emitters of
CO2, they are the obvious targets for the implementation of
carbon capture and sequestration (CCS) technologies. One
inherent challenge is that the flue gas emitted from such a power
plant is relatively dilute in CO2, with the major component being
nitrogen gas. Nanoporous metal
organic frameworks (MOFs)
have been shown to exhibit high CO2 uptake with excellent
adsorption selectively over nitrogen and other gases, and have
thus received a large amount of research interest as potential CO2
separation materials. Here zeolitic imidazolate frameworks (ZIFs),1
35
consisting of metal cations bridged by organic imidazolate anions, have
received particular attention due to their selective CO2 adsorption,1,2,7,8
excellent chemical and thermal stability,6,36 and potential for tunability
via functionalization of the organic linker groups.2,4,7,8
Uptake and selective adsorption of CO2, N2, and CH4 in ZIFs
is relevant to many applications, including natural gas recovery
and CCS,1
3,5,7,8,37
40 and a wide variety of ZIFs with different
topologies, pore/aperture sizes, and chemical functionality have
previously been developed.1
11,15,16,18,20,24,25,35 This tunability
has led to the description of ZIF synthesis as structural “design”
as opposed to materials “discovery”.7 Yet in order to develop and
synthesize ZIFs optimized for a particular application, it is
essential to have a fundamental understanding of the detailed
works.
Molecular dynamics (MD) and Monte Carlo (MC) computer
simulations are important tools for studying gas adsorption
isotherms and diffusion in porous materials such as ZIFs. The
use of accurate and physically appropriate force fields in these
simulations can provide valuable insight into the important inter-
actions between gas and framework that dictate adsorption capacity
and/or selectivity. There has been a significant amount of previous
computational work modeling the uptake and diffusion of various
gases in different ZIFs. Much of this computational work has utilized
standard “generic” force fields such as UFF41 or Drieding42 to
describe the interactions of gas molecules with the ZIF framework,
yielding mixed results and raising concerns regarding the applica-
bility of these standard force fields to these systems. Nonetheless,
many previous grand canonical Monte Carlo (GCMC) and MD
studies have examined the uptake and separation of various gases
including CO2, N2, CH4, and H2 with ZIFs, characterizing adsorp-
tion isotherms of these gases,5,38,43
57 separation and selective
adsorption of gas mixtures,44
46,49 diffusion,43
45,48,49 and impor-
tant interaction sites in the ZIFs.38,43,58
In particular, ZIF-68 and ZIF-69 have been the subject of
numerous computational studies targeting CO2 adsorption and
Received: September 27, 2011
Revised: December 9, 2011
Published: December 15, 2011

r 2011 American Chemical Society 1892 dx.doi.org/10.1021/jp209335y | J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C
separation due to their excellent capacity and selectively.2
Various force fields have been used in these studies with mixed
conclusions. For example, describing both CO2
CO2 interac-
tions and CO2
ZIF interactions using the UFF force field yields
reasonable agreement with the experimentally measured CO2
adsorption,50 although it is well-known that the UFF force field
does a poor job of describing bulk CO2
CO2 interactions. It is
therefore perhaps not surprising that utilizing either the UFF/
Drieding parameters for the CO2
ZIF interactions in conjunc-
tion with the (accurate) TraPPE59 force field for CO2
CO2
interactions led to dramatic over prediction of CO2 adsorption.48
Other authors resorted to scaling the UFF parameters describing
CO2
ZIF interactions so that interactions were less attractive,
then yielding good agreement with experimental isotherms.46
Recently it was also noted that by blocking small pores that were
deemed “inaccessible” to gas molecules, either a UFF or Drieding
description of gas-framework interaction could reproduce ex-
perimental isotherms to reasonable accuracy.47
Other notable applications of standard force fields to ZIFs
include the simulations by Perez-Pellitero et al., in which adsorp-
tion isotherms for CO2, CH4, and N2 in ZIF-8, ZIF-76, and ZIF-
69 were found to agree with experiment only after introduc-
ing empirical scaling factors of 0.69 for ε values and 0.95 for
UFF σ values,38 indicating a very significant empirical correction.
Battisti et al. utilized this same scaling of the UFF gas-framework
parameters to systematically study the adsorption and dynamics
of CO2, CH4, N2, and H2 and mixtures thereof in ZIF-2 through
ZIF-10.49 Morris et al. examined ZIFs 25, 71, 93, 96, and 97,5
using the EPM2 force field60 for CO2 and the UFF force field to
describe the framework and were for the most part able to repro-
duce the experimental trends in CO2 adsorption with function-
alization of the imidazolate linker groups, with the exception of
ZIF-96. In the latter case they found that by using OPLS-ua
parameters61 to describe the nitrile and amine groups they were
able to obtain better agreement with the experimental isotherm
for this system.
In contrast, the literature contains few examples of ab initio-
based force fields to describe gas adsorption/diffusion processes
in MOFs. Schmid and co-workers have developed ab initio force
fields to describe framework flexibility in a variety of MOFs,62
64
this being of potential importance in understanding gas diffusion in
these systems. Goddard and co-workers have parametrized func-
tional group-H2 interactions based on ab initio calculations,53,54,65,66
enabling first principles calculation of H2 uptake in MOFs doped
with metal cations. They have also used this methodology to
investigate H2 adsorption in ZIFs.53,54 Thus very little work has
focused on developing force fields tailored specifically to ZIFs, and
in nearly all cases force field construction has been limited to
deriving atomic charges from ab initio calculations and coupling
these with Lennard-Jones (LJ) parameters of a generic force field
such as UFF or Dreiding.5,38,43,47,48,50 To our knowledge, there have
not been any attempts to develop rigorous ab intio force fields for
the interaction of ZIFs with species relevant to flue gas separation.
Thus overall, previous simulations of gas uptake and selective
adsorption have often been forced to resort to arbitrary scaling
factors parametrized to prior experimental data and a patchwork
of standard force fields to achieve semi-quantitative agreement
with experiment. This is somewhat unsatisfying as this scaling
procedure may not capture the correct underlying physics. In
other words, there are likely many possible scaling procedures
(and thus many force fields) that reproduce the same isotherm,
leading to an underspecified fitting problem and the possibility of
1893
ARTICLE
“unphysical” parameters. We illustrate this principle via a simple
example, CO2 adsorption in ZIF-8. Using the EPM2 model60 for
CO2 in conjunction with UFF ZIF parameters and density
functional theory (DFT) derived charges for the ZIF-8 frame-
work (from ref 38), we locate three dramatically different param-
eter sets that all reproduce the same experimental adsorption
isotherm. For the first parameter set, we used the scaling de-
veloped by Perez-Pellitero et al.,38 a uniform scaling of σ1scale =
0.95σUFF and ε1scale = 0.69εUFF. For the second parameter set,
we use a different uniform scaling of the LJ parameters of σ2scale =
0.9σUFF and ε2scale = 0.9εUFF, and artificially modify the role of
electrostatics by scaling all charges by q2scale
i = 0.25qoriginal
i , where
qioriginal
are the original charges developed by Perez-Pellitero et al.
Note that this extreme scaling is certainly unphysical and is
merely meant to illustrate the diverse parameter sets that are
consistent with the experimental data. The third parameter set
utilizes different scalings for the imidazolate ring atoms and the
methyl functional group attached to the ring, thus modifying the
importance of the functional group in comparison to the ring
ring = 0.95σUFF and εring = 0.85εUFF for the ring
atoms: σ3scale 3scale
atoms and σmeth = 0.75σUFF and ε3scale
3scale
meth = 0.5εUFF for the methyl
atoms. The complete example parameter sets used in these
simulations are listed in Table 1. As shown in Figure 1, these
parameter sets yield very similar isotherms as predicted by
GCMC. However, they suggest dramatically different interpreta-
tions as to the importance of electrostatic and dispersive inter-
actions, as well as the role of the methyl functional group in
determining the CO2 uptake, depending on the scaling method
utilized. Furthermore, these algorithms would likely yield very
different and inconsistent results when applied to other func-
tionalized ZIFs. This inherent ambiguity when empirically
optimizing existing force fields motivates our present efforts to
develop parameter-free, ab initio force fields for nanoporous
systems; nonetheless, approximate generic force fields are still
extremely valuable for use in computational screenings, where
the availability of parameters for arbitrary systems is a principle
concern.
These considerations motivated us to develop entirely first-
principles based force fields for CO2
ZIF interactions. In this
work, we present a methodology for the development of such
force fields and, utilizing our recently developed CO2 model for
adsorbate
adsorbate interactions,67 have carried out GCMC
simulations to compute CO2 adsorption isotherms. We validate
our approach via calculations on ZIF-8 and ZIF-71, as these ZIFs
contain relatively “simple” linker groups. However the meth-
odologies developed here are equally applicable to a vast array of
existing and novel ZIFs. As in our previous work,67 the force
fields developed here rely on the use of symmetry adapted
perturbation theory (SAPT)68 to compute the interaction en-
ergies between two species. SAPT has the advantage of not only
high accuracy, but it also naturally decomposes the interaction
energy into the fundamental components of electrostatic, ex-
change, induction and dispersion interactions. This allows for the
utilization of separate, physically appropriate terms to represent
each of these interaction types. As they include essentially all of
the relevant “physics”, these physically motivated force fields
yield not only extremely accurate results but also a natural energy
decomposition allowing for greater interpretation of thermo-
dynamic predictions (adsorption isotherms) in terms of the under-
lying fundamental interactions. In order to ensure robust, phys-
ical, and asymptotically valid parameters in our force field, we obtain
parameters from monomer calculations (polarizabilities, charge
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The Journal of Physical Chemistry C ARTICLE

Table 1. Scaled UFF Parameter Sets Used to Compute the CO2 Isotherms Shown in Figure 1a

parameter set 1 parameter set 2 parameter set 3

q ε (kJ/mol) σ (Å) q ε (kJ/mol) σ (Å) q ε (kJ/mol) σ (Å)

C1 0.640 0.3033 3.259 0.160 0.3954 3.088 0.640 0.3734 3.259

C2
0.080 0.3033 3.259
0.020 0.3954 3.088
0.080 0.3734 3.259
C3
0.670 0.3033 3.259
0.168 0.3954 3.088
0.670 0.2197 2.573
H2 0.144 0.1271 2.440 0.036 0.1657 2.314 0.144 0.1565 2.440
H3 0.144 0.1271 2.440 0.036 0.1657 2.314 0.144 0.0920 1.928
N
0.540 0.1993 3.097
0.135 0.2598 2.935
0.540 0.2454 3.097
Zn 1.100 0.3582 2.338 0.275 0.4669 2.215 1.100 0.4410 2.338
a
The atom types are shown in the corresponding methyl imidazolate ring pictured in Figure 2.

Figure 2. Imidazolate atom types.

Next we discuss the various monomer calculations and fitting pro-

Figure 1. The experimental CO2/ZIF-8 isotherm at 303 K38 is shown
as the solid black dots. The GCMC predicted isotherm resulting from
the first set of parameters is depicted by the red squares and solid red
line; second set of parameters depicted by the green diamonds and green
dashed line; third set of parameters depicted by the blue triangles and
blue dotted-dashed line.
distribution, etc.) whenever possible, and fitting remaining param-
eters that rely on charge-density overlap to the SAPT interaction
energies.
We should note that many previous interaction potentials have
been derived based on SAPT interaction energy calculations,69
75
and we briefly comment on the primary differences between our
methodology and techniques used in previous works. Almost all
previous works have fit the total interaction energy between
molecules,69,70,72,74,75 while we choose to independently fit each
individual interaction energy component. This not only allows for
greater physical interpretation when such a force field is used in a
computer simulation, but also reduces the possibility of error
cancelation and helps to ensure physically meaningful parameters,
especially in larger molecules. Our procedure is probably most
similar to that of Misquitta et al.,73 with the major difference being
that we abandon the use of explicit anisotropic force field terms so
that our final force field has a form amenable to standard simulation
packages.
This paper is organized as follows: We first consider our choice
of ZIF model system, examining the transformation from an
infinite periodic ZIF crystal, to a medium sized model system
fragment (Zn2Im7Li63+), and finally to a single Li-capped imidazo-
late type ring that we utilize to obtain force-field parameters.
1894
cedures that we use to obtain the force-field parameters. Finally,
we present the GCMC simulations and the computed CO2
adsorption isotherms and discuss possible applications of this
approach to ZIF screening.
’ MODEL SYSTEM CONSTRUCTION
SAPT was used to compute the interaction energies necessary
to fit parameters in our force field. This technique is not
amenable to periodic systems, and thus our first step was to
develop a finite model system that was large enough to be
representative of the bulk crystal, but small enough to enable
tractable SAPT calculations. Our goal in constructing this model
system was to reproduce the full three-dimensional electron
density on the imidazolate rings and surrounding Zn2+ cations as
compared to the corresponding bulk. In creating this model
system, we considered a ZIF system with the simplest possible
linker group, an unfunctionalized imidazolate ring. The periodic
ZIF crystal used as a precursor was created by obtaining the XRD
crystal structure of ZIF-8 from the Cambridge Structural Data-
base (CSD), replacing the methyl groups with hydrogen. Bader
charge analysis76 was employed to characterize the electron den-
sity of the imidazolate rings in both the periodic system and the
model fragment computed utilizing the PBE density functional
with a plane wave basis (500 eV energy cutoff). The electron
density for both the model fragment and the periodic system
was computed using the VASP77,78 package. From the peri-
odic system, we constructed a Zn2Im7Li63+ fragment, where two
Zn ions were each attached to three outer imidazolate rings, and
connected through a common imidazolate ring (see the Support-
ing Information). The outer six imidazolate rings were capped
with Li ions. This system was constructed by cutting out the
appropriate fragment from the periodic system and capping the
dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C
Table 2. Comparison of Bader Charges on Imidazolate Rings
of Periodic System and Zn2Im7Li63+ Fragmenta
fragment
atom periodic central ring outer rings (average)
C1 1.062 1.075 1.061
N
1.292
1.305
1.274
N
1.292
1.300
1.353
C2 0.588 0.596 0.596
C2 0.676 0.660 0.621
H1 0.024 0.027 0.025
H2
0.180
0.155
0.119
H2
0.180
0.168
0.149
Total
0.594
0.570
0.593
a
The ring atom types are shown in Figure 2.
dangling nitrogen lone pairs with Li ions to mimic dative ligand
bonding. The Li
N bond distances were adjusted until the
Bader charges on the fragment rings matched those on the
periodic system. Shown in Table 2 is a comparison of the Bader
charges of the imidazolate rings in the Zn2Im7Li63+ fragment to
the charges of the imidazolate rings in the corresponding periodic
crystal. Comparing the electron density difference and Bader
charges for ring atoms (see the Supporting Information for
electron density difference isosurface), it is evident that the
Zn2Im7Li63+ fragment does an excellent job of reproducing the
electron density of the periodic system in the central region,
although differences obviously arise near the terminating Li
groups. Finally, a constrained geometry optimization was carried
out on the fragment, where all metal
organic bonds were kept
fixed. The main purpose for this optimization was to generate
physical C
H, C
C, and C
N bond distances and compensate
for the finite resolution of the XRD structure.
We subsequently carried out approximately 200 SAPT calcu-
lations for different configurations of CO2 interacting with the
frozen Zn2Im7Li63+ fragment. The configurations used were
taken from snapshots of an NVT MD simulation using a box
with a CO2 molecule and the Zn2Im7Li63+ fragment. The
GROMACS package79,80 was used to generate these conforma-
tions. A temperature of 3000 K was utilized to generate sampling in
repulsive regions, and the intermolecular interactions were described
using the OPLS force field61 for the fragment, and the TraPPE59 force
field for CO2; the results do not depend sensitively on the choice of
force field due to the high temperature, and our goal is to sample a
wide variety of representative intermolecular conformations. The
SAPT calculations were extremely time-consuming (4
5 days per
point on 8 processors, without computing dispersion interactions),
and are infeasible for more than one type of ZIF. However, the results
provide benchmark interaction energies against which we evaluate
smaller model systems. The details for the calculations were almost
identical to those done in our previous work.67 The density fitting
DFT-SAPT (DF-DFT-SAPT) method81
91 was used as implemen-
ted in the MolPro 2009 package.92 The PBE exchange-correlation
functional93,94 was used with an asymptotic correction, which is es-
sential for accurate interaction energies.86,91 Ionization potentials
required for the asymptotic correction were computed at the aug-cc-
pVTZ (AVTZ)/PBE0 level. We used a dimer-centered basis set
consisting of Dunning style aug-cc-pVDZ (AVDZ) basis95 for organic
atoms and def2-SVP basis96 for metal atoms (AVDZ/def2-SVP). For
twelve of these points, dispersion interactions were calculated, and as
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ARTICLE
Figure 3. Structures of Li2mIm ring (left) and Li2dcIm ring (right).
done previously,67 mid bond basis functions were used, as these are
essential to converge dispersion energies.97 Three sites were used for
the mid bond functions, with the sites placed between the CO2
molecule and the three closest imidazolate rings, and the locations
determined using the method of Podeszwa et al.74
We seek a smaller model system to reproduce the SAPT
interaction energies between the Zn2Im7Li63+ fragment and CO2
molecule (and thus the bulk-CO2 interaction). We considered
three different rings: an imidazole ring, imidazolate ring (anion),
and a Li-capped imidazolate ring (net cation), where the Li
N
bond distance for this last ring was taken to be the same as that
used in the Zn2Im7Li63+ fragment. As before, GROMACS was
used to run NVT simulations at 3000 K to generate configura-
tions for each case. Approximately 700 single-point DF-DFT-
SAPT calculations were carried out using the same methodology
as before. In contrast to the large model system, these smaller
SAPT calculations took only several processor-hours, thus
allowing for many of these calculations to be done for various
systems. Using the methodology described in the next section,
force fields were developed for each of these three ring systems.
We find that the force field generated from the small Li-
imidazolate (Li2Im) SAPT calculations, in combination with
charges for the Zn ions determined using the methodology
described below, was able to accurately reproduce the SAPT
interaction energies between CO2 and the larger Zn2Im7Li63+
fragment (see the Supporting Information). We thus utilize Li-
capped imidazolate-type rings in all subsequent calculations to
efficiently generate force fields for various bulk ZIFs.
’ FORCE FIELD DEVELOPMENT
Based on the above results, we developed corresponding small
model systems for ZIF-8 and ZIF-71. For ZIF-8, a Li-capped
methyl-imidazolate ring (Li2mIm) was used and for ZIF-71 a Li-
capped dichloro-imidazolate ring (Li2dcIm) was employed
(see Figure 3). As described above, ∼700 single-point DF-DFT-
SAPT calculations with different CO2 configurations were carried
out for each imidazolate-type ring system. We utilized a dimer cen-
tered AVTZ/def2-TZVPP basis plus midbond functions, yielding
SAPT interaction energies closely approximating the basis set limit.
The midbond basis consisted of the same basis functions as before,
located at the center of mass of the dimer. Unless explicitly stated,
only parameters corresponding to imidazolate ring/substituent
atoms were fit, while the CO2 parameters were taken from our pre-
vious work.67 Using a similar methodology as before,67 we separately
fit each physically distinct term in our force field to the correspond-
ing SAPT term in our calculations. We believe that this approach not
only results in a more robust force field with physically accurate
parameters, but also allows for greater insight and analysis when
such a force field is used in simulations.
All fitting in this paper, unless otherwise explicitly stated,
utilized a least mean square error approach, in which parameters
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The Journal of Physical Chemistry C
were explicitly constrained to exhibit the appropriate symmetry
of the ring, with χ2 = ∑ni W(ESAPT,tot
i )(ESAPT,comp
i
EMM,comp
i )2
SAPT,comp
where Ei is the desired SAPT interaction energy com-
ponent for data point i, EMM,comp
i is the corresponding energy
component predicted by the force field, and W(ESAPT,tot i )
is a weighting function for each data point depending on the
total interaction energy for that configuration. The weighting
function was used to make the fit insensitive to high-energy
repulsive points (which are unlikely to be sampled at relevant
temperatures) and was of the Fermi-Dirac form
1 combination rule, Aexch
WðEÞ ¼
expððE
μÞ=kB TÞ þ 1
where μ was typically chosen to be 5 mHartree and kBT was
chosen to be 1 mHartree (∼300 K).
We have taken many steps to reduce the correlation of param-
eters during force field fitting, which is necessary to ensure the
resulting parameters are physically meaningful and transferable.
Using physical considerations and obtaining parameters from
monomer calculations whenever possible, we rely on SAPT inter-
action energies only for fitting terms explicitly involving electron
overlap (e.g., exponential, Buckingham-like terms, vide infra).
Nonetheless, we have found cases where there is coupling between
Buckingham coefficients on neighboring atoms when fitting inter-
action energies. Therefore, while fitting all Buckingham coefficients
on functionalized imidazolate rings, we have introduced weak
harmonic constraints for carbon, nitrogen, hydrogen, and lithium
atoms. The values around which parameters were constrained were
determined from corresponding fits to SAPT calculations for a Li-
capped unfunctionalized imidazolate ring interacting with a CO2
molecule. For each energy component, only four atomic parameters
were used, namely those for the four atom types mentioned above.
In order to determine the uniqueness of the unfunctionalized
imidazolate ring fits, we analyzed the fit of Buckingham terms for the
exchange energy. We constructed a covariance matrix, describing
the sensitivity of the fit of the data points to percentage changes in
the parameters. Small eigenvalues of this covariance matrix indicate
that the parameters are under-determined due to coupling, and the
corresponding eigenvectors describe the coupling of these param-
eters. We therefore characterized the change in rms error of the fit
with a change in parameter space along the eigenvector of the
covariance matrix corresponding to the smallest eigenvalue. We
found a 5% increase in rms error with an average change of 20
25%
of each parameter along this eigenvector. Therefore, we expect these
parameters to be qualitatively accurate and physically meaningful for
use as atomic base values, and thus all subsequent fits utilized these
resulting parameters to center the harmonic constraints for similar
atom types. The magnitude of the constraint is very weak, leading to
rms errors in the energy fits that were negligibly different for
constrained and unconstrained fits.
The SAPT interaction energy decomposition is as follows:
ð1Þ ð1Þ ð2Þ ð2Þ ð2Þ
Eint ¼ Epol þ Eexch þ Eind þ Eind
exch þ Edisp
ð2Þ
þ Edisp
exch þ Eδhf
To fit the first order exchange repulsion energy, E(1) exch, we
utilized a pairwise additive Buckingham functional form
ð1Þ
Eexch = ∑i, j Aexch
ij expð
Bij rij Þ
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ARTICLE
where the index i runs over all atoms on the imidazolate-type ring
and j runs over the three atoms of the CO 2 molecule. The
exponents,Bij, were determined using the procedure used
previously.67 Briefly, initial pairwise exponents, B0ij, were deter-
mined using atomic ionization potentials which describe the
asymptotic exponential decay of atomic electron densities. Then,
the prefactors A exch ij along with a scaling factor, λ, such that
B ij = λB 0ij, were fit to the SAPT first-order exchange interac-
tion energies. Note that for the Aexch ij prefactors (and all other
similar Buckingham prefactors used in the other interaction energy
terms), only atomic ring parameters Aexch ii were fit, and a standard
= (Aexch exch 1/2
ij ii Ajj ) , was used to generate the
pairwise parameters. For CO2, the Ajj parameters were taken from
our previous work.67 As before,67 a scale factor of λ ≈ 1.2 was found,
and the final exponents Bij were used accordingly in all other
Buckingham terms for the remaining energy components.
The electrostatic term, E(1) pol , was fit using a combination of screened
atom-centered point charges and Buckingham-type terms to account
for charge penetration. The atom-centered point charges were
obtained as follows. First, the electron density of the imidazolate-type
ring was computed using the same level of theory as used for the
SAPT calculations, and a distributed multipole analysis (DMA)98,99
was carried out using the Molpro package.92 Using the method
proposed by Ferenczy,100 atom centered point charges were fit to
represent these distributed multipole moments. Fitting atomic charges
to DMA generated multipole moments rather than the electrostatic
potential (ESP) leads to negligible differences in reproducing the ESP,
but has the advantage of resulting in more transferable charges and
prevents unphysical charges on “buried” atoms.101,102 The final
functional form used to fit the electrostatic SAPT term was
qi qj
ð1Þ
Epol = ∑
i, j
f1 ðBij , rij Þ
rij ∑
þ
i, j
ij expð
Bij rij Þ
Aelec
For the screening function, the Tang
Toennies functional
form103 was used
n ðλrÞm
fn ðλ, rÞ ¼ 1
e
λr ∑
m¼0 m!
where the parameters required for the screening function were
taken to be the exponents used in all Buckingham terms, λ = Bij,
as both screening and Pauli repulsion arise from electron cloud
overlap. The atomic ring parameters Aelec ii , required to generated
the pairwise Aelec parameters, were then fit to reproduce the
ij
SAPT first-order electrostatic energies. As the penetration terms
for electrostatics were attractive in nature, the combination rule
Aelec =
(Aelec elec 1/2
ij ii Ajj ) was used.
The second order polarization/induction energy, E(2) (2)
pol = Eind +
Eind
exch, was fit using an explicitly polarizable treatment for CO2.
(2)
This explicit polarization was accomplished with the use of a shell
model, and is described in our previous work.67 All intermolecular
charge
charge interactions, whether static or shell, were screened
using the Tang-Toennies function as described above. The screen-
ing parameters for the shells were taken to be the same as those used
for the corresponding atoms. All intramolecular charge
charge
interactions (due to polarization) were screened with a Thole-type
function104 as described previously.67 No explicit polarization was
used for the ZIF framework. The total functional form used to
model the induction energy is
ð2Þ
Epol = Ushell þ ∑i, j Aindij expð
BijrijÞ
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The Journal of Physical Chemistry C
Here, Ushell is defined as the difference between the energy of the
system with optimized shell positions, and that of the corresponding
nonpolarizable system. The atomic ring parameters, Aind jj , required
ij parameters were fit to reproduce the SAPT
for the pairwise Aind
second-order polarization/induction energy, E(2)
pol . As with electro-
statics, it was found that the penetration terms for induction were
ij =
(Aii Ajj )
attractive in nature, and the combination rule Aind ind ind 1/2
was used to generate the pairwise parameters. Since the shell
model can exhibit overpolarization in strong electric fields,105
and the capping Li atoms are formally cations, configurations of
CO2 close to Li exhibit induction energies that are incapable of
being fit with the shell model; we omit these data points (using a
methodology described below) in our fits to yield more physical
Aind
ij parameters. It is important to note that this problem with
the shell model only arises due to the ionic nature of the Li-
capped imidazolate-type rings that we use to generate param-
eters for the ZIF systems, and as the ZIF crystals contain only
buried cationic centers we do not anticipate these problems in
simulations of such systems.
The second-order dispersion energy, E(2) (2) (2)
VdW = Edisp + Edisp
exch,
was fit using a combination of steps to arrive at an accurate and
physically meaningful parameter set; here a na€ive fit directly to
the SAPT energies yields ambiguous results due to the long-
range nature of dispersion and thus strong coupling between
atomic parameters. We thus employ the approach developed by
Williams and Stone,106 as implemented in the CAMCASP
program,107
110 to compute distributed imaginary frequency-
dependent polarizabilities and obtain atomic C6, C8, and C10
dispersion parameters. For these monomer calculations we used
an AVTZ basis with an asymptotically corrected PBE0 exchange-
correlation functional. The linear response employs an ALDAX +
CHF kernel, meaning 25% exact Hartree
Fock exchange was
used, consistent with the amount present in the PBE0 functional
(see CAMCASP manual for further discussion). This methodol-
ogy was used to compute atomic C6, C8, and C10 dispersion
parameters for CO2 and the Li2dcIm and Li2mIm imidazolate-
type rings (our previous bulk CO2 force field67 did not utilize
C8 or C10 terms). The pairwise dispersion parameters, Cij0 n were
then generated using the combination rule Cij0 ii0 jj0 1/2
n = (Cn Cn )
where the atomic parameters Cii0 n were those computed using
CAMCASP. A notable exception to this rule was for hydrogen-
heavy atom pairwise parameters. Here, consistent with literature
recommendation,109 only atomic C6 parameters were computed
for hydrogen atoms, and therefore the nonzero C8 parameter for
such pairs was given by CHyd
Heavy0
8 = (CHyd0
6 CHeavy0
10 )1/2, which
is a consistent definition when noting the rank of the polariz-
ability tensors involved in computing each Cn term.
As with the induction energy fit, we found it best to remove
points from the SAPT data set in which the CO2 molecule was
“too close” to either Li atom of the imidazolate type ring. The
data points were removed by estimating the dispersion energy of
each configuration using the parameters from the CAMCASP
calculations; data points were removed if either Li atom of the
imidazolate type ring was the main contributor to the dispersion
interaction energy. For all other energy components, only
Buckingham coefficients were fit, accounting for charge pen-
etration effects. The dispersion energy, in addition to fitting
Buckingham coefficients, was also used to fit two scale factors,
one of which adjusts the magnitude of the asymptotic C6
C10
terms. As the C6
C10 treatment of dispersion becomes unphy-
sical in charge penetration regions, we found it best to remove
said data points for this fit.
ARTICLE
The final functional form used to reproduce the SAPT
dispersion energies is
Cij
ð2Þ
EVdW = ∑i, j Adisp
ij expð
Bij rij Þ
∑ ∑ fn ðβij , rij Þ nn
rij
n ¼ 6, 8, 10 i, j
Here, we have included two scale factors such that βij = λdampBij
and Cijn = λasympCij0n . Both of these scale factors, as well as atomic
Adisp
ii ring parameters, were fit to the SAPT imidazolate-type
ring/CO2 dispersion interaction energies and thus are not
empirically determined. Similar to the treatments of electro-
statics and induction, the pairwise combination rule Adisp ij =

(Adisp disp 1/2
ii Ajj ) was used. Because of the noted sensitivity of
the CO2 isotherms to dispersion parameters, we added a penalty
function to the typical least mean square error fitting approach.
This penalty function was proportional to the absolute mean
deviation of the fitted energies to the SAPT values, and the
purpose of this penalty function was to prevent any systematic
error in the fit. Also, to ensure that the correct asymptotic
behavior was preserved, rather than constructing the χ2 function
using the absolute energy differences, we used the percentage
energy deviations. This ensured that small dispersion energies
were fit accurately; although small in magnitude, these weak
interactions contribute significantly to bulk adsorption due to the
corresponding increase in the volume element at large distances.
Because our previous CO2 model67 used a different treatment
for dispersion, we obtained new atomic parameters for CO2
consistent with this new functional form. This was done by
refitting the previously computed SAPT CO2
CO2 dispersion
interaction data67 using the functional form and methodology
discussed above. The final dispersion energy fits utilized a scale
factor λasymp that was typically ∼1.05, indicating that the
Cijn parameters used in the force field were typically 5% greater than
those predicted by the CAMCASP calculations (possibly due to
basis set size as well as order of polarizability tensors utilized109).
The scale factor λdamp used to scale the “exponents” for the
Tang
Toennies damping function was typically ∼0.9, which in
combination with the original ∼1.2 scaling of the exponents from
, their asymptotic values, led to damping exponents very close to
those predicted by the exact asymptotic atomic densities.
The delta Hartree
Fock terms, Eδhf, have been described
previously67,86 and were fit using exponential functions
Eδhf = ∑i, j Aδhf
ij expð
Bij rij Þ
The atomic ring parameters Aδhf jj were fit to reproduce the
calculated Eδhf interaction energies, using a slightly different
combination rule to generate the pairwise parameters Aδhf ij . The
combination rule used here was Aδhf δhf δhf 1/2
ij = (|Aii ||Ajj |) , where
the sign of Aδhf δhf δhf
ij was determined to be positive if Aii Ajj was
positive, and negative otherwise.
All fits for the Li2mIm and Li2dcIm ring systems are given in
the Supporting Information (sections 3 and 4) as are the
complete set of parameters generated by these fits.
Finally, we note one possible potential improvement in our
force field fitting methodology. For intermolecular configura-
tions that are closer than the potential minimum (i.e., on the
repulsive “wall”), the total interaction energy results from
cancellation of substantially larger individual interaction energy
components. Thus small errors (<5%) in individual energy
components can result in non-trivial errors in total energy. As
these configurations involve significant charge penetration, the
1897 dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C ARTICLE

associated errors are likely related to our approximations in The resulting parameters for both ZIF-8 and ZIF-71 are sum-
accounting for complex charge penetration effects in individual marized in the tables below.
interaction terms. Note that we would almost always expect these Finally, it is worth emphasizing that, despite the technical
configurations to be unimportant in a typical simulation since nature of the fitting procedure outlined above, the resulting force
they involve short inter-molecular distances and thus typically field is of the relatively simple function form
high total energies. However, at high temperatures or for specific
qq
ZIF topologies it is conceivable that these points may contribute
non-trivially to the Boltzmann-weighted ensemble. In this case,
Utot ¼ ∑i, j f1 ðBij, rij Þ riij j
we suggest that it may be preferable to revert to utilizing a !
piecewise-defined potential, utilizing a different functional form Cij
to describe these very shortest distances under the constraint of þ ∑i, j Atot
ij expð
Bij rij Þ
∑
n ¼ 6, 8, 10
fn ðβij , rij Þ nn
rij
continuity and differentiability of the total potential.
Force fields for bulk ZIF-8 and ZIF-71 were constructed by
treating Zn atoms as bare point charges (since they are fully þ Ushell
coordinated, buried, and cationic), and using the parameters
developed for the Li2 mIm and Li2 dcIm ring systems respec- consisting of electrostatics, Buckingham (exponential) short-
tively, for the remaining organic atoms. Atomic charges are range repulsion, damped dispersion, and Drude oscillator polar-
obtained using DMA analysis on slightly larger models ization. This makes it straightforward to implement in existing
systems. Starting with the Zn2 Im7 Li6 3+ fragment, we con- standard simulation packages, such as GROMACS79,80 or
structed Zn 2 mIm7 Li6 3+ and Zn2 dcIm7 Li6 3+ fragment sys- Towhee.111
tems easily by functionalizing the imidazolate rings. A sub-
sequent DMA followed by a fit to point charges (as before) Table 4. Force Field Parameters for ZIF-71a
was carried out for both Zn 2mIm7 Li 6 3+ and Zn2 dcIm 7Li6 3+
atom type i C1 C2 Cl H1 N1 Zn
fragments. Note that the charges resulting from the DMA
naturally yield a nearly perfect electrically neutral bulk q(e) 0.5934 0.3886
0.1139 0.0609
0.9992 1.5894
stoichiometric material, and thus no adjustment was neces-
Carbon
sary. These charges were then used for the simula-
tions involving ZIF-8 and ZIF-71 respectively (Figure 4). Atot (kJ/mol)/104 6.381 5.051 17.227 1.144 10.650 0.000
B (Å
1) 3.222 3.222 3.351 3.392 3.448 3.917
C6 [kJ/(mol Å6)]/102 10.501 17.440 23.721 5.642 9.286 0.000
C8 [kJ/(mol Å8)]/103 7.715 19.351 15.327 3.642 14.922 0.000
C10 [kJ/(mol Å10)]/104 2.807 10.636 4.878 0.000 11.760 0.000
Oxygen
tot 4
A (kJ/mol)/10 12.125 9.064 23.952 2.421 19.259 0.000
B (Å
1) 3.396 3.396 3.554 3.603 3.672 4.293
C6 [kJ/(mol Å
6)]/102 8.734 14.505 19.729 4.692 7.723 0.000
C8 [kJ/(mol Å
8)]/103 4.326 10.851 8.595 1.334 8.367 0.000
C10 [kJ/(mol Å10)]/104 1.028 3.894 1.786 0.000 4.306 0.000
a
After the charges are listed, the cross-parameters are listed for the
Figure 4. Atom types for imidazolate rings in ZIF-8 (left) and ZIF-71 carbon atom of CO2, followed by the cross-parameters for the oxygen
(right). atoms of CO2.

Table 3. Force Field Parameters for ZIF-8a

atom type i C1 C2 C3 H2 H3 N Zn

q(e) 0.6786 0.1198
0.1498 0.1182 0.0682
1.0135 1.6352

Carbon
Atot (kJ/mol)/104 4.474 6.636 6.129 1.076 1.199 10.573 0.000
B (Å
1) 3.222 3.222 3.222 3.392 3.392 3.448 3.917
C6 [kJ/(mol Å6)]/102 10.033 16.076 18.381 2.344 2.384 10.448 0.000
C8 [kJ/(mol Å8)]/103 12.097 15.223 15.286 1.513 1.539 14.607 0.000
C10 [kJ/(mol Å10)]/104 7.355 7.063 6.165 0.000 0.000 9.914 0.000
Oxygen
Atot (kJ/mol)/104 7.859 10.483 8.823 1.405 1.844 19.296 0.000
B (Å
1) 3.396 3.396 3.396 3.603 3.603 3.672 4.293
C6 [kJ/(mol Å
6)]/102 8.344 13.371 15.288 1.950 1.983 8.690 0.000
C8 [kJ/(mol Å
8)]/103 6.783 8.536 8.571 0.554 0.563 8.191 0.000
C10 [kJ/(mol Å10)]/104 2.693 2.586 2.257 0.000 0.000 3.630 0.000
a
After the charges are listed, the cross-parameters are listed for the carbon atom of CO2, followed by the cross-parameters for the oxygen atoms of CO2.

1898 dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903

The Journal of Physical Chemistry C
Figure 5. CO2 adsorption isotherm in ZIF-8 at 303 K. Experimental
results from ref 38 are shown as black squares. Simulation results from
this work are shown as the red circles.
’ RESULTS AND DISCUSSION
GCMC simulations were carried out to compute CO2 adsorp-
tion isotherms in ZIF-8 and ZIF-71 and validate our parameter-
free force fields. Our recently developed CO2 model, which has
been derived in a similar fashion and benchmarked against
various bulk CO2 properties, was used to describe CO2
CO2
interactions.67 The unit cell of ZIF-8 was obtained from the CSD
crystal structure, and the refined unit cell of ZIF-71 was obtained
from the authors of ref 5. For ZIF-8, a box consisting of 2  2  2
unit cells was used so as to allow for a longer real space cutoff for
the calculation of dispersion terms. It has been shown that using
experimental ZIF XRD crystal structures in GCMC simulations
leads to results comparable to using DFT optimized structures, as
long as the XRD crystal structure does not contain ambiguous
atom positions.48 We utilize a rigid treatment of ZIF atom
positions for both simulations, which we believe is justified since
we are computing room temperature isotherms at relatively low
pressures. We note that previous observations of ZIF-8 frame-
work structure changes due to gas adsorption have occurred at
either much higher pressures or much lower temperatures.112
Framework flexibility may play an important role in transport
properties, particularly with bulky adsorbates, although we
examine strictly equilibrium properties in the present work.
Since we use a shell model for CO2, all shell positions have to
be reoptimized whenever any CO2 molecule is moved. This
makes single-molecule translation/rotation moves extremely
inefficient. We thus utilize a GCMC simulation with hybrid
MD/MC translational/rotational moves.113 In this hybrid ap-
proach, we randomly select center-of-mass and angular velocities
from a Maxwell
Boltzmann distribution for each attempted
move, compute the forces and torques on all CO2 molecules, and
numerically integrate Newton’s equations of motion to generate
a new trial move in which all CO2 molecules in the system have
been displaced. Here the only criterion is that the integrator must
be reversible (energy conservation is not required), and we utilize
the velocity Verlet method, with a typical time step of ∼50 fs. In
conjunction with these hybrid translation/rotation moves, we
utilize standard single particle insertion/deletion techniques to
complete the GCMC approach. The particle-mesh Ewald (PME)114
technique is used to treat electrostatics, with a real space cutoff of
1899
ARTICLE
Figure 6. CO2 adsorption isotherm in ZIF-71 at 298 K. Experimental
results from ref 5 are shown as the black squares. Simulation results
utilizing the UFF force field also from ref 5 are shown as the blue squares.
Simulation results from this work are shown as the red circles.
10 Å. For the long-range part of the Buckingham potential, we use a
cutoff of 14 Å  for ZIF-71 and 16 Å  for ZIF-8, these cutoffs being
dictated by the size of the unit cell (or super cell); no additional long-
range correction is used due to the inhomogeneous nature of the sys-
tem. We utilize a conjugate gradient algorithm115 to optimize the shell
positions at every step. Particle insertions and deletions were attempt-
ed with equal probability, and the combination of these moves
accounted for 20% of all trial moves, with the remaining 80% of
moves being hybrid MD/MC type displacements.
The calculated CO2 adsorption isotherms for ZIF-8 and ZIF-
71 are shown in Figures 5 and 6, respectively. The nonideality
dependence of the chemical potential of CO2 at various pressures
was accounted for using the Peng
Robinson equation of state.
For both ZIFs, we find good agreement with the experimental
isotherms. It is important to note that these force fields have been
generated entirely from ab initio calculations, demonstrating the
potential to predict CO2 adsorption in ZIFs completely from first
principles without resorting to arbitrary “scaling” to fit previously
measured experimental results.
We can trivially analyze the contributions of the distinct types
of physical interactions to the average interaction energy con-
tributing to CO2 adsorption in these ZIFs under representative
conditions. This energy decomposition is an intrinsic feature of
the physically motivated force field, with distinct terms in our
force field used to represent these different types of physical
interactions. Shown in Figure 7 are the percentage contributions
to the total interaction energies for ZIF-8 and ZIF-71 at condi-
tions close to STP. It is evident that both these systems are
dispersion dominated, emphasizing the importance of obtaining
the correct physical description for this term in the force fields.
The fact that electrostatics (and thus induction) plays a more
minor role in the adsorption is in part due to the fact that both
ZIF-8 and ZIF-71 are constructed with symmetrically function-
alized imidazolate linker rings. As pointed out by Morris et al.,5
ZIFs with symmetrically functionalized linker groups tend to
produce weaker electrostatic fields in their cavities than do
similar ZIFs with asymmetric functionalization. Therefore, we
believe that electrostatic and induction interactions will be of
greater importance in other, asymmetric ZIFs, and we believe
that our use of DMA to obtain physical atomic charges and the
dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C
explicit treatment of many-body induction effects through our
shell model for CO2 will be increasingly important for such cases.
A comparison of the volumetric CO2 uptakes in ZIF-8 and
ZIF-71 given by our simulations is shown in Figure 8 (note these
are at slightly different temperatures corresponding to the
experimental conditions). From these isotherms, we gain insight
on the effect of functionalization of the imidazolate rings on the
CO2 uptake. At pressures less than ∼3 bar, the isotherms show
that ZIF-71, with imidazolate rings “functionalized” with chlorine
atoms, exhibits greater CO2 uptake than ZIF-8 which has
imidazolate rings “functionalized” with a single methyl group.
At low pressures, gas uptake should be dominated by the
magnitude of the binding energies at attractive sites, and indeed
our simulations give average adsorption energies of
14.14 and

19.41 kJ/mol for a CO2 molecule in ZIF-8 and ZIF-71,
respectively (at conditions of ∼300 K, 1 bar). At pressures
greater than ∼5 bar we find that ZIF-8 starts to exhibit slightly
higher uptake than ZIF-71, most likely due to the former’s higher
free volume (experimental BET surface areas are ∼650 m2/g for
ZIF-715 and ∼1450 m2/g for ZIF-8, with similar topologies;38
note that FZIF8/FZIF71 ≈ 0.8).
CO2 density plots in ZIF-8, showing the most CO2 density (and
thus the most probable adsorption sites) from the Monte Carlo
Figure 7. Percentage contributions of distinct physical terms with
respect to the total interaction energy under representative conditions,
including all CO2
CO2 interactions and CO2
framework interactions.
Simulations were run at ∼1 bar, ∼300 K for both ZIFs. ZIF-8 is shown in
blue, and ZIF-71 is shown in red. Components which are attractive are
shown as positive percentage contributions, while repulsive contribu-
tions are represented as negative percentages.
Figure 8. Comparison of ZIF-8 and ZIF-71 computed isotherms. The ZIF-8 isotherm (left) is at 303 K, while the ZIF-71 isotherm (right) is at 298 K.
Note the slight difference in temperatures, corresponding to the experimental conditions. Both isotherms show absolute gas uptakes.
1900
ARTICLE
simulation are presented in Figure 9 (generated using the VMD
software116). We find that this density plot is very similar to the
one computed by Perez-Pellitero et al.38 (as can be verified by
comparing the (100) perspective to the identical perspective in
ref 38). The prominent adsorption sites are on either side of the
six-membered ring aperture between cages in the ZIF crystal.
Three of the six methyl-imidazolate rings comprising the aper-
ture have their methyl groups oriented along the aperture, and a
typical configuration shows a CO2 molecule close (∼3 Å) to one
of these methyl groups. To analyze the energetics controlling the
binding at such sites, a short NVT-ensemble simulation was run
at 200K with one CO2 molecule initially positioned at this
interaction site. This low temperature is chosen so that the
molecule would not desorb from this site, thus allowing us to
analyze the binding energetics at this single site. We find an
average total adsorption energy of 16
17 kJ/mol for such sites,
with attraction dominated by dispersion (roughly 2.5:1/disper-
sion to electrostatics). This is consistent with the findings of
Perez-Pellitero et al.,38 where it was noted that the main adsorp-
tion sites match the regions of maximal “van der Waals” inter-
actions. However note that our electrostatic energy accounts for
charge penetration effects, whereas Perez-Pellitero’s treatment
does not. It is also interesting to note that these prominent
interaction sites are the same as those found for methane
adsorption in ZIF-8 by Wu et al.40 using neutron diffraction
(as can be verified by comparing the (111) perspective to the
identical perspective in ref 40). As the electrostatic interaction
between methane and the ZIF-8 framework is weak, the fact that
Figure 9. CO2 density plots in ZIF-8: left (100) perspective; right (111)
perspective.
dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C
Figure 10. CO2 density plots in ZIF-71: left (100) perspective; right
(111) perspective.
the ZIF-8 adsorption sites are the same for both methane and
CO2 further supports the conclusion that this process is disper-
sion dominated.
The ZIF-71 cages have faces (apertures) consisting of four, six,
or eight imidazolate-type rings, and the CO2 density plots shown
in Figure 10 indicate that all of these faces act as important
interaction sites. However, similar to ZIF-8, it is seen that the
principle adsorption sites are on either side of the six ring
apertures. We characterize the adsorption at these specific sites
via a 200 K simulation, as before, yielding an average total
adsorption energy of 24
25 kJ/mol. At these sites, the interac-
tion is even more dispersive, roughly 4:1/dispersion to electro-
statics. This somewhat surprising absence of enhanced elec-
trostatics is further illustrated by examining the DMA derived
atomic charges on the ring atoms (given in the Supporting
Information), where we see a partial charge on the chlorine
atoms of only ∼
0.1 au This result can be explained by the
symmetry of the functionalization as stated before, as well as
possibly by the proximity of the chlorine atoms to the nitrogen
atoms of the imidazolate ring. Comparing these important
absorption sites in ZIF-71 to those in ZIF-8, we see the same
correlation between dispersion dominated interactions and the
preference for interaction with six ring aperture sites. We also
note that the six ring sites have significantly greater adsorption
energies (a difference of ∼8 kJ/mol) in ZIF-71 compared to
ZIF-8, which might be expected due to the chlorine atoms on the
imidazolate rings of ZIF-71. The fact that this enhancement is
primarily due to dispersive interactions might be somewhat
unexpected, however. In this context the ability to rigorously
separate different interaction components through the use of a
physically decomposed force field is essential for the accurate
interpretation of the effects of functionalization.
The observed semiquantitative to quantitative agreement with
the corresponding experimental isotherms validates the accuracy
of our force fields and the general, parameter-free approach to
generating them. In conjunction with our previous correspond-
ing results for bulk CO2, they also reaffirm our broader metho-
dology for obtaining robust and physically motivated force field
parameters. Although the ZIFs studied in this work are relatively
“simple” (i.e., minimally functionalized), they provide proof of
concept for the force field development methods that we have
used. The resulting natural energy decomposition yields chemi-
cal insight into the properties of ZIFs that contribute to high CO2
adsorption. Given the extensive tunability of ZIFs, this enhanced
understanding of physical interactions is crucial in order to
efficiently develop new and better systems for CCS.
1901
ARTICLE
The primary limitation of the present approach is that it
requires parametrization for each individual ZIF/MOF system,
which would make their use in computational screening quite
challenging. In this sense, it is important to note that transferable
“generic” force fields do play an extremely important role in the
computational screening of MOFs. Due to their simplicity and
the fact that no new parameters need to be developed, such force
fields can be used to quickly screen many MOFs for a particular
gas adsorption application.117,118 Although the predictions from
these force fields may not always be accurate (as seen in ZIF-8
with unscaled UFF parameters), they provide initial “first pass”
information that can be valuable to narrow down either further
computation investigation with more accurate models or experi-
mental characterization. It is thus important to recognize the
limitations of both standard “generic” force fields (e.g., accuracy)
and system-specific ab inito force fields (e.g., transferability).
We are currently working to bridge this divide by developing
transferable ab initio force fields tailored to specific classes of
materials, e.g. functionalized ZIFs, thus incorporating the best
strengths of both approaches; these efforts will be the subject of
future publications.
’ CONCLUSION
We have developed parameter-free ab initio force fields
tailored to describe the interactions between CO2 and ZIFs,
specifically ZIF-8 and ZIF-71. These physically motivated force
fields are novel in that they contain separate terms to explicitly
account for the distinct types of physical interactions, namely
exchange, electrostatic, induction, and dispersion. We have made
the effort to ensure physically meaningful parameters in our force
fields, obtaining as many parameters as possible based on isolated
molecular properties, and relying on SAPT interaction energy
calculations to obtain parameters that are related to the overlap of
charge densities. Using these novel force fields, we find excellent
agreement with experimental CO2 adsorption isotherms for both
of these systems, with both systems being dominated by disper-
sion interactions, and electrostatic interactions playing a smaller
role partially due to the symmetry of the functionalized imida-
zolate linker rings in each ZIF.
Overall, the approach outlined in the present work offers
several compelling advantages over the use of standard, empirical
force fields. Most significantly, our methodology generates force
fields entirely from ab initio SAPT calculations with absolutely no
empirical parameters. Thus although the present work focuses on
two minimally functionalized ZIFs, the methodology outlined
here is entirely general and easily extensible to novel and/or
highly functionalized ZIFs (or even adsorption of other gases,
e.g., N2). In contrast, previous approaches have often relied on a
patchwork of force fields or empirical scale factors based on
postfacto comparison with experiment. Furthermore, our newly
generated force fields are extremely accurate, yielding semiquan-
titative to quantitative accuracy, surpassing the level required for
purposes of computational screening. Finally, we note that the
physically motivated nature of these force fields admits a natural
energy decomposition, expressing the interaction energy in
“chemical” terms such as exchange, electrostatics, polarization,
and dispersion. By allowing for the analysis of simulation results
under representative conditions in chemically intuitive terms, the
present developments will lay the groundwork for intelligent
synthesis and design of novel ZIFs for CO2 sequestration and
other gas adsorption applications.
dx.doi.org/10.1021/jp209335y |J. Phys. Chem. C 2012, 116, 1892–1903
The Journal of Physical Chemistry C
’ ASSOCIATED CONTENT
bS Supporting Information. Figure comparing the electron
density of the imidazolate rings of the Zn2Im7Li63+ fragment
and those of the corresponding periodic system. Figures show-
ing SAPT energy fits for the Zn2Im7Li63+ fragment and a CO2
molecule. Tables giving parameters used in CO2-ZIF-8 force
field. Figures showing SAPT energy fits for a Li2mIm ring and a
CO2 molecule used to derive CO2-ZIF-8 force field parameters.
Tables giving parameters used in CO2-ZIF-71 force field.
Figures showing SAPT energy fits for a Li2dcIm ring and a
CO2 molecule used to derive CO2-ZIF-71 force field param-
eters. This material is available free of charge via the Internet at
http://pubs.acs.org.
’ AUTHOR INFORMATION
Author Contributions
† (27) Rettig, S. J.; Sanchez, V.; Storr, A.; Thompson, R. C.; Trotter, J.
These authors contributed equally to this work.
’ ACKNOWLEDGMENT
We thank Brian Laird for providing us with simulation data for
various ZIFs (including ZIF-71). This research was supported by
the National Science Foundation through TeraGrid resources
provided by Purdue University and via Grant CHE-0840494.119
Additional computing resources were provided via the Center for
High Throughput Computing at the University of Wisconsin120
and by National Science Foundation Grant CHE-0840494. This
research was supported by DOE (DE-FG02-09ER16059).
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