Grand-canonical quantized liquid density-functional theory in a Car-Parrinello implementation

Walther, Christian F. J.; Patchkovskii, Serguei; Heine, Thomas

doi:10.1063/1.4813122

Cited by 4 publications

(11 citation statements)

References 45 publications

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“…The members of the IRMOF series share the same connecting SBU, but different organic linkers provide a systematic variation of pore size. The series of isoreticular MOFs studied in this work are IRMOF-n with n=1, 4,6,8,9,10,12,14,16,18 is derived from linking the octahedral zinc acetate unit Zn 4 O(CO 2 ) 6 , with a variety of linear ditopic carboxylates 4,31 (see Figure 1). MOF-177 is constructed from the same connecting SBU and the tritopic BTB linker.…”

Section: Computational Methods and Models Of The Materialsmentioning

confidence: 99%

“…However, we introduce a pseudo-wavefunction that satisfies the equation ρ( r) =ψ 2 ( r). The main purpose of this wave function is to be able to approximate the kinetic energy operator, which we can now conveniently write within the effective one particle approximation 14 :…”

Section: Quantized Liquid Density-functional Theorymentioning

confidence: 99%

“…After validating our computational approach for IRMOF-1, we apply QLDFT within the same setup as for IRMOF-1 to assess hydrogen adsorption properties at T = 77 K on a series of IRMOFs (IRMOF-n with n = 1,4,6,8,9,10,12,14,16,18) and MOF-177. In Table I, we list the total gravimetric and volumetric adsorption capacities at 20, 40, 60, 80 and 100 bars, and the excess adsorption at saturation condition.…”

Section: Hydrogen Adsorption In the Irmof Series And Mof-177mentioning

confidence: 99%

“…The QLDFT method has been successfully applied in the hydrogen adsorption studies in carbon foams, 13 porous aromatic frameworks (PAFs) 21 and to determine the selectivity of D 2 vs. H 2 adsorption in the metal-organic framework MFU-4. 22 A low-temperature alternative to the Kohn-Sham scheme of QLDFT has been suggested recently 14 : due to the bosonic nature of molecular hydrogen, at low temperatures the lowest eigenstate dominates the occupation of the Kohn-Sham Hamiltonian. Thus, the quantum-mechanical problem was reformulated within the Hohenberg-Kohn-Mermin formalism of a Grand Canonical (GC) ensemble.…”

Section: Quantized Liquid Density-functional Theorymentioning

confidence: 99%

“…Quantum effects can then be included either by semi-classical correction (Feynman-Hibbs (FH)), 11 or directly included into the Hamiltonian as kinetic energy operator. [12][13][14] We further benchmark our approach and assess the different approximations by their influence on the adsorption properties of the H 2 quantum fluid. Finally, after careful validation on MOF-5, we apply our method, the Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) to a series of MOFs.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

Wahiduzzaman

Walther

Heine

2014

The Journal of Chemical Physics

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The role of nuclear quantum effects on the adsorption of molecular hydrogen in metal-organic frameworks (MOFs) has been investigated on grounds of Grand-Canonical Quantized Liquid Density-Functional Theory (GC-QLDFT) calculations. For this purpose, we have carefully validated classical H2-host interaction potentials that are obtained by fitting Born-Oppenheimer ab initio reference data. The hydrogen adsorption has first been assessed classically using Liquid Density-Functional Theory and the Grand-Canonical Monte Carlo methods. The results have been compared against the semi-classical treatment of quantum effects by applying the Feynman-Hibbs correction to the Born-Oppenheimer-derived potentials, and by explicit treatment within the GC-QLDFT. The results are compared with experimental data and indicate pronounced quantum and possibly many-particle effects. After validation calculations have been carried out for IRMOF-1 (MOF-5), GC-QLDFT is applied to study the adsorption of H2 in a series of MOFs, including IRMOF-4, -6, -8, -9, -10, -12, -14, -16, -18, and MOF-177. Finally, we discuss the evolution of the H2 quantum fluid with increasing pressure and lowering temperature.

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Section: Computational Methods and Models Of The Materialsmentioning

confidence: 99%

Section: Quantized Liquid Density-functional Theorymentioning

confidence: 99%

Section: Hydrogen Adsorption In the Irmof Series And Mof-177mentioning

confidence: 99%

Section: Quantized Liquid Density-functional Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

Wahiduzzaman

Walther

Heine

2014

The Journal of Chemical Physics

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Monte Carlo Study of a Planar Electric Double Layer Formed by Ions with Off-Center Charge

et al. 2017

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Grand canonical Monte Carlo simulation results are reported for an electric double layer (EDL) modeled by a planar charged hard wall, hard sphere cations with an off-center charge, and spherical anions with a charge at the center of the sphere. The ion charge numbers are Z = +1 and Z = -1, and the diameter, d, of a hard sphere is the same for anions and cations. The ions are immersed in a solvent mimicked by a continuum dielectric medium at standard temperature. The results are obtained for three values of charge displacement, s = d/16, d/4, 7d/16 from the center of the sphere and the following electrolyte concentrations: 0.5, 1.0, 2.0, and 3.0 M. The profiles of electrode-ion singlet distributions, cation reduced charge density, angular function, and mean electrostatic potential are reported for an electrode surface charge density σ = -0.30 C m, whereas the electrode potential and the differential capacitance of EDL are shown as functions of the electrode charge density varying from -1.00 to +1.00 C m. At negative electrode charges and with increasing values of the charge separation, the differential capacitance curve rises. As the electrolyte concentration increases, the shape of the differential capacitance curve changes from that of a minimum surrounded by two maxima into that of a distorted single maximum.

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Highly Effective Hydrogen Isotope Separation in Nanoporous Metal–Organic Frameworks with Open Metal Sites: Direct Measurement and Theoretical Analysis

et al. 2014

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Separating gaseous mixtures that consist of very similar size is one of the critical issues in modern separation technology. Especially, the separation of the isotopes hydrogen and deuterium requires special efforts, even though these isotopes show a very large mass ratio. Conventionally, H/D separation can be realized through cryogenic distillation of the molecular species or the Girdler-sulfide process, which are among the most energy-intensive separation techniques in the chemical industry. However, costs can be significantly reduced by using highly mass-selective nanoporous sorbents. Here, we describe a hydrogen isotope separation strategy exploiting the strongly attractive open metal sites present in nanoporous metal-organic frameworks of the CPO-27 family (also referred to as MOF-74). A theoretical analysis predicts an outstanding hydrogen isotopologue separation at open metal sites due to isotopal effects, which has been directly observed through cryogenic thermal desorption spectroscopy. For H2/D2 separation of an equimolar mixture at 60 K, the selectivity of 12 is the highest value ever measured, and this methodology shows extremely high separation efficiencies even above 77 K. Our theoretical results imply also a high selectivity for HD/H2 separation at similar temperatures, and together with catalytically active sites, we propose a mechanism to produce D2 from HD/H2 mixtures with natural or enriched deuterium content.

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Grand-canonical quantized liquid density-functional theory in a Car-Parrinello implementation

Cited by 4 publications

References 45 publications

Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

Hydrogen adsorption in metal-organic frameworks: The role of nuclear quantum effects

Monte Carlo Study of a Planar Electric Double Layer Formed by Ions with Off-Center Charge

Highly Effective Hydrogen Isotope Separation in Nanoporous Metal–Organic Frameworks with Open Metal Sites: Direct Measurement and Theoretical Analysis

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