Noncovalent Interactions by Quantum Monte Carlo

Dubecký, Matúš; Mitáš, Luboš; Jurečka, Petr

doi:10.1021/acs.chemrev.5b00577

Cited by 128 publications

(164 citation statements)

References 269 publications

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“…Monte Carlo (QMC), [44][45][46] and density functional theory (DFT). [47][48][49][50] Each method offers different strengths in computational accuracy, expense, and model complexity.…”

Section: Introduction To Theoretical Methodsmentioning

confidence: 99%

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Allendorf

Hulvey

Gennett

et al. 2018

Energy Environ. Sci.

217

187

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Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H 2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H 2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed. IntroductionStorage of hydrogen with sufficient gravimetric and volumetric capacity for vehicular use remains a significant obstacle to the widespread adoption of hydrogen fuel cell electric vehicles (FCEVs). Several FCEV models are now commercially available in limited locations around the world, and in these vehicles hydrogen is stored as a gas at room temperature with a fill Table 1 along with the current performance of 700 bar systems. These values pertain to the entire storage system, which includes the mass and volume of hydrogen in addition to the tank and associated balance-ofplant (BOP) components. Notably, it is physically impossible to meet the 2025 and ultimate volumetric capacity target with pressurized gas, as the density of H 2 gas at 700 bar and room temperature is just 40 g L À1 without accounting for the BOP.The search for solid-state H 2 storage materials that can supplant compressed gas systems has been ongoing for at least two decades. The development of a viable storage material Broader contextThe widespread use of hydrogen as a clean, sustainable energy carrier has the potential to provide several significant benefits, including a reduction in oil dependency and emissions, improved energy security and grid resiliency, and substantial economic opportunities across many sectors. Hydrogen-fueled vehicles are already appearing internationally, and one of the critical enabling technologies for increasing their availability is on-board hydrogen storage. Stakeholders in developing a hydrogen in...

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“…Monte Carlo (QMC), [44][45][46] and density functional theory (DFT). [47][48][49][50] Each method offers different strengths in computational accuracy, expense, and model complexity.…”

Section: Introduction To Theoretical Methodsmentioning

confidence: 99%

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Allendorf

Hulvey

Gennett

et al. 2018

Energy Environ. Sci.

217

187

View full text Add to dashboard Cite

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“…24 CCSD(T) can be applied to complexes having up to around 35 heavy atoms, while MP2.5 can handle systems up to twice the size. Unfortunately, however, no reference method of comparable quality is currently available for use with periodic models, with the exception of the stochastic quantum Monte Carlo method, 22,26,27 that embody exceeding computational demands.…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite

Karlický

Otyepková

et al. 2017

J. Chem. Theory Comput.

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Understanding strength and nature of noncovalent binding to surfaces imposes significant challenge both for computations and experiments. We explored the adsorption of five small nonpolar organic molecules (acetone, acetonitrile, dichloromethane, ethanol, ethyl acetate) to fluorographene and fluorographite using inverse gas chromatography and theoretical calculations, providing new insights into the strength and nature of adsorption of small organic molecules on these surfaces. The measured adsorption enthalpies on fluorographite range from −7 to −13 kcal/mol and are by 1–2 kcal/mol lower than those measured on graphene/graphite, which indicates higher affinity of organic adsorbates to fluorographene than to graphene. The dispersion-corrected functionals performed well, and the nonlocal vdW DFT functionals (particularly optB86b-vdW) achieved the best agreement with the experimental data. Computations show that the adsorption enthalpies are controlled by the interaction energy, which is dominated by London dispersion forces (∼70%). The calculations also show that bonding to structural features, like edges and steps, as well as defects does not significantly increase the adsorption enthalpies, which explains a low sensitivity of measured adsorption enthalpies to coverage. The adopted Langmuir model for fitting experimental data enabled determination of adsorption entropies. The adsorption on the fluorographene/fluorographite surface resulted in an entropy loss equal to approximately 40% of the gas phase entropy.

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“…[23][24][25] Previous studies have shown that diffusion quantum Monte Carlo (DMC) can provide accurate energies for noncovalent interactions systems. [26][27][28][29][30] DMC can also produce an accurate description of the phase diagram of materials under pressure. [31][32][33] In general, QMC-based methods are faster than the most accurate post-Hartree-Fock schemes for large number of particles N. The computational cost of QMC methods scales usually as N 3 -N 4 depending on the method.…”

Section: Introductionmentioning

confidence: 99%

Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

Azadi

Cohen

2016

The Journal of Chemical Physics

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We studied the low-pressure (0–10 GPa) phase diagram of crystalline benzene using quantum Monte Carlo and density functional theory (DFT) methods. We performed diffusion quantum Monte Carlo (DMC) calculations to obtain accurate static phase diagrams as benchmarks for modern van der Waals density functionals. Using density functional perturbation theory, we computed the phonon contributions to the free energies. Our DFT enthalpy-pressure phase diagrams indicate that the Pbca and P21/c structures are the most stable phases within the studied pressure range. The DMC Gibbs free-energy calculations predict that the room temperature Pbca to P21/c phase transition occurs at 2.1(1) GPa. This prediction is consistent with available experimental results at room temperature. Our DMC calculations give 50.6 ± 0.5 kJ/mol for crystalline benzene lattice energy

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Noncovalent Interactions by Quantum Monte Carlo

Cited by 128 publications

References 269 publications

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Adsorption of Organic Molecules to van der Waals Materials: Comparison of Fluorographene and Fluorographite with Graphene and Graphite

Low-pressure phase diagram of crystalline benzene from quantum Monte Carlo

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