Abstract
Whereas grand-canonical Monte Carlo (GCMC) simulations based on generic force fields provide good predictions of adsorption isotherms in metal-organic frameworks (MOFs), especially at higher temperature, they fail to correctly describe the adsorption mechanism in MOFs with coordinatively unsaturated sites (cus's) at low temperatures, even for nonpolar fluids such as methane. To address this problem, we directly implemented the potential energy surface calculated by a hybrid DFT/ab inito method in the GCMC simulations using the adsorption of methane on CuBTC as an example. A comparison with previously published in situ experiments shows that our approach not only quantitatively predicts adsorption isotherms for a wide range of temperatures and pressures but also provides the correct description of the adsorption mechanism, including adsorption on the cus's. We also show that care must be taken when selecting the ab initio method to be coupled with GCMC simulations to obtain accurate predictions.
| Original language | English |
|---|---|
| Pages (from-to) | 23074-23080 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry C |
| Volume | 115 |
| Issue number | 46 |
| DOIs | |
| Publication status | Published - 24 Nov 2011 |
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Accurate prediction of methane adsorption in a metal-organic framework with unsaturated metal sites by direct implementation of an ab initio derived potential energy surface in GCMC simulation. / Chen, Linjiang; Grajciar, Lukáš; Nachtigall, Petr; Düren, Tina.
In: Journal of Physical Chemistry C, Vol. 115, No. 46, 24.11.2011, p. 23074-23080.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Accurate prediction of methane adsorption in a metal-organic framework with unsaturated metal sites by direct implementation of an ab initio derived potential energy surface in GCMC simulation
AU - Chen, Linjiang
AU - Grajciar, Lukáš
AU - Nachtigall, Petr
AU - Düren, Tina
PY - 2011/11/24
Y1 - 2011/11/24
N2 - Whereas grand-canonical Monte Carlo (GCMC) simulations based on generic force fields provide good predictions of adsorption isotherms in metal-organic frameworks (MOFs), especially at higher temperature, they fail to correctly describe the adsorption mechanism in MOFs with coordinatively unsaturated sites (cus's) at low temperatures, even for nonpolar fluids such as methane. To address this problem, we directly implemented the potential energy surface calculated by a hybrid DFT/ab inito method in the GCMC simulations using the adsorption of methane on CuBTC as an example. A comparison with previously published in situ experiments shows that our approach not only quantitatively predicts adsorption isotherms for a wide range of temperatures and pressures but also provides the correct description of the adsorption mechanism, including adsorption on the cus's. We also show that care must be taken when selecting the ab initio method to be coupled with GCMC simulations to obtain accurate predictions.
AB - Whereas grand-canonical Monte Carlo (GCMC) simulations based on generic force fields provide good predictions of adsorption isotherms in metal-organic frameworks (MOFs), especially at higher temperature, they fail to correctly describe the adsorption mechanism in MOFs with coordinatively unsaturated sites (cus's) at low temperatures, even for nonpolar fluids such as methane. To address this problem, we directly implemented the potential energy surface calculated by a hybrid DFT/ab inito method in the GCMC simulations using the adsorption of methane on CuBTC as an example. A comparison with previously published in situ experiments shows that our approach not only quantitatively predicts adsorption isotherms for a wide range of temperatures and pressures but also provides the correct description of the adsorption mechanism, including adsorption on the cus's. We also show that care must be taken when selecting the ab initio method to be coupled with GCMC simulations to obtain accurate predictions.
UR - http://www.scopus.com/inward/record.url?scp=81755177580&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1021/jp2090878
U2 - 10.1021/jp2090878
DO - 10.1021/jp2090878
M3 - Article
VL - 115
SP - 23074
EP - 23080
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 46
ER -