Modelling the interaction of molecular hydrogen with lithium-doped hydrogen storage materials

Kolmann, Stephen J.; Chan, Bun; Jordan, Meredith J. T.

doi:10.1016/j.cplett.2008.10.081

Cited by 63 publications

(60 citation statements)

References 44 publications

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“…Similarly to of the +1 positive charge is "lost" to benzene. 16 Although other computational simulations of Li-doped MOF materials also show large localised positive charge on the lithium, in some cases larger than the +0.7 e found for H 2 -Li + -benzene, 50 we suggest that our ∆H ads = −14.5…”

Section: Adsorption Enthalpy ∆H Adsmentioning

confidence: 94%

“…We therefore investigated zero Kelvin properties of H 2 adsorbed to Li + -benzene-a model system for Li-doped MOF and carbon-based hydrogen storage materials-using reduced-dimensional rigid-body diffusion Monte Carlo (RBDMC) simulations on modified Shepard interpolated potential energy surfaces (PESs) constructed at either the M05-2X/6-31+G(d,p) or M05-2X/6-311+G(2df,p) levels of theory. 16 We had previously benchmarked the density functional calculations to more accurate coupled cluster calculations. 16 Consistent with inelastic neutron scattering spectra of H 2 adsorbed to a graphite intercalation compound, KC 24 , 17 we found that, at 0 K, there was quantum delocalisation of the H 2 molecule and, consistent with previous theory 18 and experiment, 19 the zero point energy difference upon binding is a significant fraction of the electronic binding energy, in this case 35 %.…”

Section: Introductionmentioning

confidence: 99%

“…16 We had previously benchmarked the density functional calculations to more accurate coupled cluster calculations. 16 Consistent with inelastic neutron scattering spectra of H 2 adsorbed to a graphite intercalation compound, KC 24 , 17 we found that, at 0 K, there was quantum delocalisation of the H 2 molecule and, consistent with previous theory 18 and experiment, 19 the zero point energy difference upon binding is a significant fraction of the electronic binding energy, in this case 35 %. 20 We also found that the "helicopter" and "ferris wheel" motions of the adsorbed H 2 molecule were significantly anharmonic and could be modelled as free and hindered rotors, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials

Lindoy

Kolmann

D’Arcy

et al. 2015

The Journal of Chemical Physics

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Finite temperature quantum and anharmonic effects are studied in H 2 -Li + -benzene, a model hydrogen storage material, using path integral Monte Carlo (PIMC) simulations on an interpolated potential energy surface (PES) refined over the eight intermolecular degrees of freedom based upon M05-2X/6-311+G(2df,p) density functional theory calculations. Rigidbody PIMC simulations are performed at temperatures ranging from 77 K to 150 K, producing both quantum and classical probability density histograms describing the adsorbed H 2 . Quantum effects broaden the histograms with respect to their classical analogues and increase the expectation values of the radial and angular polar coordinates describing the location of the center-of-mass of the H 2 molecule. The rigid-body PIMC simulations also provide estimates of the change in internal energy, ∆U ads , and enthalpy, ∆H ads , for H 2 adsorption onto Li + -benzene, as a function of temperature. These estimates indicate that quantum effects are important even at room temperature and classical results should be interpreted with caution. Our results also show that anharmonicity is more important in the calculation of U and H than coupling-coupling between the intermolecular degrees of freedom becomes less important as temperature increases whereas anharmonicity becomes more important. The most anharmonic motions in H 2 -Li + -benzene are the "helicopter" and "ferris wheel" H 2 rotations. Treating these motions as one-dimensional free and hindered rotors, respectively, provides simple corrections to standard harmonic oscillator, rigid rotor thermochemical expressions for internal energy and enthalpy that encapsulate the majority of the anharmonicity. At 150 K, our best rigid-body PIMC estimates for ∆U ads and ∆H ads are −13.3 ± 0.1 and −14.5 ± 0.1 kJ.mol −1 , respectively. a) Electronic

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Section: Adsorption Enthalpy ∆H Adsmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials

Lindoy

Kolmann

D’Arcy

et al. 2015

The Journal of Chemical Physics

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“…However, it has been shown that similar decorations can bind more than one guest molecule. 15,[17][18][19][20][21]29,58,59,61 We now seek to bind several guest molecules per decoration and thus maximize the overall molecule uptake. To keep the gravimetric storage density high, we focus on the Li decoration only and study as an example the binding of several H 2 molecules.…”

Section: High-loading Case Of Hydrogenmentioning

confidence: 99%

“…organolithium nanostructures 15 and other Li-decorated MOFs, [20][21][22]29,61 see the Supplemental Material.…”

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confidence: 99%

Fivefold increase of hydrogen uptake in MOF74 through linker decorations

et al. 2016

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We present ab initio results for linker decorations in Mg-MOF74-i.e. attaching various metals M = Li, Na, K, Sc, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Pd, Ag, and Pt near the ring of the linker-creating new strong adsorption sites and thus maximizing small molecule uptake. We find that in most cases these decorations influence the overall form and structure of Mg-MOF74 only marginally. After the initial screening we chose metals that bind favorably to the linker and further investigate adsorption of H2, CO2, and H2O for M = Li, Na, K, and Sc. For the case of H2 we show that up to 24 additional guest molecules can be adsorbed in the MOF unit cell, with binding energies comparable to the original open-metal sites at the six corners of the channel. This leads to a 5-fold increase of the molecule uptake in Mg-MOF74, with tremendous impact on many applications in general and hydrogen storage in particular-where the gravimetric hydrogen density increases from 1.63 mass% to 7.28 mass% and the volumetric density from 15.10 g H2 L −1 to 75.50 g H2 L −1 .

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Lithiumdotierung eines hydroxymodifizierten MIL‐53‐Strukturanalogons zur Verbesserung der Wasserstoffadsorption

2009

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Modelling the interaction of molecular hydrogen with lithium-doped hydrogen storage materials

Cited by 63 publications

References 44 publications

Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials

Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials

Fivefold increase of hydrogen uptake in MOF74 through linker decorations

Lithiumdotierung eines hydroxymodifizierten MIL‐53‐Strukturanalogons zur Verbesserung der Wasserstoffadsorption

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