The virial stress tensor-based instantaneous heat flux, which is used by LAMMPS, is only valid for the small subset of simulations that contain only pairwise interactions. For systems that contain ...many-body interactions using 3- or 4-body potentials, a more complete derivation is required. We have created a software patch to LAMMPS that implements the correct heat flux calculation approach for 3- and 4-body potentials, based on the derivation by Torii et al. ( J. Chem. Phys. 2008, 128, 044504 ) Using two example systems, the error in the uncorrected code for many-body potential heat flux is shown to be significant and reaches nearly 100% of the many-body potential heat flux for the systems we studied; hence, the error of the total heat flux calculation is proportional to the fraction of the total heat flux transferred through the many-body potentials. This error may have consequences for thermal conductivities calculated using the Green–Kubo method or any NEMD method that uses the instantaneous heat flux. We recommend that all researchers using LAMMPS for heat flux calculations where significant heat is transferred via the many-body potentials adopt the corrected code.
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Although metal–organic frameworks (MOFs) are promising materials for gas storage and separation applications, the heat released during the exothermic adsorption process can potentially negatively ...impact their practical utility. Thermal transport in MOFs has not been widely studied, and among the relatively few reports on the topic, MOFs have either been assumed to be defect free or the presence of defects was not discussed. However, defects naturally exist in MOFs and can also be introduced intentionally. Here, we investigate the effect of missing linker defects on the thermal conductivity of HKUST-1 using molecular dynamics (MDs) simulation and the Green–Kubo method. We found that missing linker defects, even at low concentrations, substantially reduce the thermal conductivity of HKUST-1. If not taken into account, the presence of defects could lead to significant discrepancies between experimentally measured and computationally predicted thermal conductivities.
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We have studied the mechanisms of heat transfer in a porous crystal-gas mixture system, motivated by the not insignificant challenge of quickly dissipating heat generated in metal-organic frameworks ...(MOFs) due to gas adsorption. Our study reveals that the thermal conductance of the system (crystal and gas) is dominated by lattice thermal conductivity in the crystal, and that conductance is reduced as the concentration of gas in the pores increases. This mechanism was observed from classical molecular simulations of a monatomic gas in an idealized porous crystal structure. We show that the decreased conductivity associated with increased gas concentration is due to phonon scattering in the crystal due to interactions with gas molecules. Calculations of scattering rates for two phonon modes reveal that scattering of the lowest frequency mode scales linearly with gas density. This result suggests that the probability of a phonon-gas collision is simply proportional to the number of gas molecules in the pore.
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Metal-organic frameworks (MOFs) are porous materials constructed from modular molecular building blocks, typically metal clusters and organic linkers. These can, in principle, be assembled to form an ...almost unlimited number of MOFs, yet materials reported to date represent only a tiny fraction of the possible combinations. Here, we demonstrate a computational approach to generate all conceivable MOFs from a given chemical library of building blocks (based on the structures of known MOFs) and rapidly screen them to find the best candidates for a specific application. From a library of 102 building blocks we generated 137,953 hypothetical MOFs and for each one calculated the pore-size distribution, surface area and methane-storage capacity. We identified over 300 MOFs with a predicted methane-storage capacity better than that of any known material, and this approach also revealed structure-property relationships. Methyl-functionalized MOFs were frequently top performers, so we selected one such promising MOF and experimentally confirmed its predicted capacity.
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Polymeric membranes are being studied for their potential use in post-combustion carbon capture on the premise that they could dramatically lower costs relative to mature technologies available ...today. Mixed matrix membranes (MMMs) are advanced materials formed by combining polymers with inorganic particles. Using metal–organic frameworks (MOFs) as the inorganic particles has been shown to improve selectivity and permeability over pure polymers. We have carried out high-throughput atomistic simulations on 112 888 real and hypothetical metal–organic framework structures in order to calculate their CO 2 permeabilities and CO 2 /N 2 selectivities. The CO 2 /H 2 O sorption selectivity of 2 017 real MOFs was evaluated using the H 2 O sorption data of Li et al. (S. Li, Y. G. Chung and R. Q. Snurr, Langmuir , 2016, 32 , 10368–10376). Using experimentally measured polymer properties and the Maxwell model, we predicted the properties of all of the hypothetical mixed matrix membranes that could be made by combining the metal–organic frameworks with each of nine polymers, resulting in over one million possible MMMs. The predicted gas permeation of MMMs was compared to published gas permeation data in order to validate the methodology. We then carried out twelve individually optimized techno-economic evaluations of a three-stage membrane-based capture process. For each evaluation, capture process variables such as flow rate, capture fraction, pressure and temperature conditions were optimized and the resultant cost data were interpolated in order to assign cost based on membrane selectivity and permeability. This work makes a connection from atomistic simulation all the way to techno-economic evaluation for a membrane-based carbon capture process. We find that a large number of possible mixed matrix membranes are predicted to yield a cost of carbon capture less than $50 per tonne CO 2 removed, and a significant number of MOFs so identified have favorable CO 2 /H 2 O sorption selectivity.
Abstract
Whether the presence of adsorbates increases or decreases thermal conductivity in metal-organic frameworks (MOFs) has been an open question. Here we report observations of thermal transport ...in the metal-organic framework HKUST-1 in the presence of various liquid adsorbates: water, methanol, and ethanol. Experimental thermoreflectance measurements were performed on single crystals and thin films, and theoretical predictions were made using molecular dynamics simulations. We find that the thermal conductivity of HKUST-1 decreases by 40 – 80% depending on the adsorbate, a result that cannot be explained by effective medium approximations. Our findings demonstrate that adsorbates introduce additional phonon scattering in HKUST-1, which particularly shortens the lifetimes of low-frequency phonon modes. As a result, the system thermal conductivity is lowered to a greater extent than the increase expected by the creation of additional heat transfer channels. Finally, we show that thermal diffusivity is even more greatly reduced than thermal conductivity by adsorption.
Given that energy (exciton) migration in natural photosynthesis primarily occurs in highly ordered porphyrin-like pigments (chlorophylls), equally highly ordered porphyrin-based metal–organic ...frameworks (MOFs) might be expected to exhibit similar behavior, thereby facilitating antenna-like light-harvesting and positioning such materials for use in solar energy conversion schemes. Herein, we report the first example of directional, long-distance energy migration within a MOF. Two MOFs, namely F-MOF and DA-MOF that are composed of two Zn(II) porphyrin struts 5,15-dipyridyl-10,20-bis(pentafluorophenyl)porphinatozinc(II) and 5,15-bis4-(pyridyl)ethynyl-10,20-diphenylporphinatozinc(II), respectively, were investigated. From fluorescence quenching experiments and theoretical calculations, we find that the photogenerated exciton migrates over a net distance of up to ∼45 porphyrin struts within its lifetime in DA-MOF (but only ∼3 in F-MOF), with a high anisotropy along a specific direction. The remarkably efficient exciton migration in DA-MOF is attributed to enhanced π-conjugation through the addition of two acetylene moieties in the porphyrin molecule, which leads to greater Q-band absorption intensity and much faster exciton-hopping (energy transfer between adjacent porphyrin struts). The long distance and directional energy migration in DA-MOF suggests promising applications of this compound or related compounds in solar energy conversion schemes as an efficient light-harvesting and energy-transport component.
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An Extended Charge Equilibration Method Wilmer, Christopher E; Kim, Ki Chul; Snurr, Randall Q
The journal of physical chemistry letters,
09/2012, Volume:
3, Issue:
17
Journal Article
Peer reviewed
We present a method for estimating partial atomic charges that uses all of the measured ionization energies (first, second, third, etc.) for every atom in the periodic table. We build on the charge ...equilibration (Qeq) method of Rappé and Goddard (which used only the first ionization energies) but reduce the number of ad hoc parameters from at least one for every type of atom to just two global parameters: a dielectric strength and a modified parameter for hydrogen atoms. Periodic electrostatic interactions are calculated via Ewald sums, and the partial charges are determined by simultaneously solving a system of linear equations; no iteration is required. We compare the predicted partial atomic charges of this extended charge equilibration (EQeq) scheme against plane-wave density-functional theory derived charges determined via the REPEAT method for 12 diverse metal–organic frameworks (MOFs). We also compare EQeq charges against ChelpG charges calculated using nonperiodic MOF fragments, as well as against Qeq charges as implemented in Accelrys Materials Studio. We demonstrate that for the purpose of ranking MOFs from best to worst for carbon capture applications, EQeq charges perform as well as charges derived from electrostatic potentials, but EQeq requires only a tiny fraction of the computational cost (seconds vs days for the MOFs studied). The source code for the EQeq algorithm is provided.
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There is an urgent need to identify porous materials that can efficiently separate CO sub(2) from mixtures of gases, such as the exhaust of fossil-fuel-based power plants and from impure sources of ...CH sub(4) (e.g., natural gas and landfill gas). Recently, researchers have investigated collections of porous metal-organic frameworks (MOFs) with the intent of finding correlations between CO sub(2) separation ability and various material properties. However, due to the limited size of the collections, no clear correlations were found for material properties such as pore size, surface area, and pore volume, leaving researchers with little guidance in the design of new materials. In this work we drastically expand the scope of previous studies to include over 130 000 hypothetical MOFs, using molecular simulation to generate the adsorption properties. The resulting data exhibit sharply defined structure-property relationships that were not apparent when smaller collections of MOFs were considered. We show clear correlations between purely structural characteristics (e.g., pore size, surface area, and pore volume), as well as chemical characteristics (i.e., functional groups), with five adsorbent evaluation criteria taken from the engineering literature. These reported structure-property relationships can serve as a map for experimental synthesis going forward.
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