In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1
We study the permeation dynamics of helium and carbon dioxide through an atomistically detailed model of a polymer of intrinsic microporosity, PIM-1, via non-equilibrium molecular dynamics (NEMD) simulations. This work presents the first explicit molecular modeling of gas permeation through a high f...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2015-03-01
|
| Series: | Membranes |
| Subjects: | |
| Online Access: | http://www.mdpi.com/2077-0375/5/1/99 |
| id |
doaj-708d6d25c1754bd89e21ad448c5facc5 |
|---|---|
| record_format |
Article |
| spelling |
doaj-708d6d25c1754bd89e21ad448c5facc52020-11-24T23:41:24ZengMDPI AGMembranes2077-03752015-03-01519911910.3390/membranes5010099membranes5010099In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1Hendrik Frentrup0Kyle E. Hart1Coray M. Colina2Erich A. Müller3Department of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UKDepartment of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USADepartment of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USADepartment of Chemical Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ, UKWe study the permeation dynamics of helium and carbon dioxide through an atomistically detailed model of a polymer of intrinsic microporosity, PIM-1, via non-equilibrium molecular dynamics (NEMD) simulations. This work presents the first explicit molecular modeling of gas permeation through a high free-volume polymer sample, and it demonstrates how permeability and solubility can be obtained coherently from a single simulation. Solubilities in particular can be obtained to a very high degree of confidence and within experimental inaccuracies. Furthermore, the simulations make it possible to obtain very specific information on the diffusion dynamics of penetrant molecules and yield detailed maps of gas occupancy, which are akin to a digital tomographic scan of the polymer network. In addition to determining permeability and solubility directly from NEMD simulations, the results shed light on the permeation mechanism of the penetrant gases, suggesting that the relative openness of the microporous topology promotes the anomalous diffusion of penetrant gases, which entails a deviation from the pore hopping mechanism usually observed in gas diffusion in polymers.http://www.mdpi.com/2077-0375/5/1/99gas permeationglassy polymersolutiondiffusionmolecular dynamicsnon-equilibriumsimulation |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Hendrik Frentrup Kyle E. Hart Coray M. Colina Erich A. Müller |
| spellingShingle |
Hendrik Frentrup Kyle E. Hart Coray M. Colina Erich A. Müller In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 Membranes gas permeation glassy polymer solution diffusion molecular dynamics non-equilibrium simulation |
| author_facet |
Hendrik Frentrup Kyle E. Hart Coray M. Colina Erich A. Müller |
| author_sort |
Hendrik Frentrup |
| title |
In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 |
| title_short |
In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 |
| title_full |
In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 |
| title_fullStr |
In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 |
| title_full_unstemmed |
In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1 |
| title_sort |
in silico determination of gas permeabilities by non-equilibrium molecular dynamics: co2 and he through pim-1 |
| publisher |
MDPI AG |
| series |
Membranes |
| issn |
2077-0375 |
| publishDate |
2015-03-01 |
| description |
We study the permeation dynamics of helium and carbon dioxide through an atomistically detailed model of a polymer of intrinsic microporosity, PIM-1, via non-equilibrium molecular dynamics (NEMD) simulations. This work presents the first explicit molecular modeling of gas permeation through a high free-volume polymer sample, and it demonstrates how permeability and solubility can be obtained coherently from a single simulation. Solubilities in particular can be obtained to a very high degree of confidence and within experimental inaccuracies. Furthermore, the simulations make it possible to obtain very specific information on the diffusion dynamics of penetrant molecules and yield detailed maps of gas occupancy, which are akin to a digital tomographic scan of the polymer network. In addition to determining permeability and solubility directly from NEMD simulations, the results shed light on the permeation mechanism of the penetrant gases, suggesting that the relative openness of the microporous topology promotes the anomalous diffusion of penetrant gases, which entails a deviation from the pore hopping mechanism usually observed in gas diffusion in polymers. |
| topic |
gas permeation glassy polymer solution diffusion molecular dynamics non-equilibrium simulation |
| url |
http://www.mdpi.com/2077-0375/5/1/99 |
| work_keys_str_mv |
AT hendrikfrentrup insilicodeterminationofgaspermeabilitiesbynonequilibriummoleculardynamicsco2andhethroughpim1 AT kyleehart insilicodeterminationofgaspermeabilitiesbynonequilibriummoleculardynamicsco2andhethroughpim1 AT coraymcolina insilicodeterminationofgaspermeabilitiesbynonequilibriummoleculardynamicsco2andhethroughpim1 AT erichamuller insilicodeterminationofgaspermeabilitiesbynonequilibriummoleculardynamicsco2andhethroughpim1 |
| _version_ |
1725507405833306112 |