arXiv subjects

A. Rabdel Ruiz-Salvador

Publications and source records attributed to A. Rabdel Ruiz-Salvador.

5 recordsLinked to original sources

arXiv2026

A topology-tuned pressure valve across the isoreticular RHO zeolite family

The isoreticular index of the eight-member embedded RHO zeolite hierarchy operates as a phenomenological design knob that tunes the mechanical critical pressure of the framework valve from $\sim 0.94$ GPa for parent RHO down to a predicted $\lesssim 0.03$ GPa for the largest member PST-28, more than an order of magnitude lower across a single family of synthesizable nanoporous solids. The molecular-valve effect that defines zeolite RHO (a reversible centric-to-acentric phase transition triggered by water, gas pressure, or mechanical loading) is shown here to be not a peculiarity of the smallest member but a generic property of the whole hierarchy, with a critical pressure that decays exponentially with the isoreticular order $k$. Combining lattice dynamics, full elastic-constant tensors, and finite-temperature free-energy reconstructions within a classical core-shell description of the pure-silica frameworks (independently validated against r$^2$SCAN+rVV10 density-functional theory on $G_1$ and $G_2$), we find that the entire family is well described by an effective mean-field Landau picture in which the framework distortion couples quadratically to the volumetric strain. We emphasise that $p_c$ is a mechanical (hydrostatic) critical pressure of the bare pure-silica framework, used as a proxy for the intrinsic framework softness and for the cation- and dehydration-driven response of the real aluminosilicates; it is not a gas-adsorption pressure. The exponential extrapolation places $p_c(G_6\text{-}G_8) \lesssim 0.1$ GPa (model-dependent band $0.03$-$0.15$ GPa), identifying the higher-order members as the softest, most stimuli-responsive frameworks of the hierarchy; whether this intrinsic softness translates into guest-driven switching at low gas activities will depend on the Al distribution, extra-framework cations and adsorbed molecules, and remains to be tested experimentally.

cond-mat.mtrl-sci↗

arXiv2018

Atomic charges for modeling metal-organic frameworks: Why and how

Atomic partial charges are parameters of key importance in the simulation of Metal-Organic Frameworks (MOFs), since Coulombic interactions decrease with the distance more slowly than van der Waals interactions. But despite its relevance, there is no method to unambiguously assign charges to each atom, since atomic charges are not quantum observables. There are several methods that allow the calculation of atomic charges, most of them starting from the wavefunction or the electronic density or the system, as obtained with quantum mechanical calculations. In this work, we describe the most common methods employed to calculate atomic charges in MOFs. In order to show the influence that even small variations of structure have on atomic charges, we present the results that we obtained for DMOF-1. We also discuss the effect that small variations of atomic charges have on the predicted structural properties IRMOF-1.

cond-mat.mtrl-sci↗

arXiv2016

Controlling Thermal Expansion: a Metal Organic Frameworks Route

Controlling thermal expansion is an important, not yet resolved, and challenging problem in materials research. A conceptual design is introduced here for the first time, for the use of MOFs as platforms for controlling thermal expansion devices that can operate in the negative, zero and positive expansion regimes. A detailed computer simulation study, based on molecular dynamics, is presented to support the targeted application. MOF-5 has been selected as model material along with three molecules of similar size and known differences in terms of the nature of host--guest interactions. It has been shown that adsorbate molecules can control, in a colligative way, the thermal expansion of the solid, so that changing the adsorbate molecules induces the solid to have positive, zero or negative thermal expansion. We analyze in-depth the distortion mechanisms, beyond the ligand metal junction to cover the ligand distortions, and the energetic and entropic effect on the thermo-structural behavior. We provide an unprecedented atomistic insight on the effect of adsorbates on the thermal expansion of MOFs, as a basic tool towards controlling the thermal expansion.

cond-mat.mtrl-sci↗

arXiv2016

Understanding Nanopore Window Distortions in the Reversible Molecular Valve Zeolite RHO

Molecular valves are becoming popular for potential biomedical applications. However, little is known concerning their performance in energy and environmental areas. Zeolite RHO shows unique pore deformations upon changes in hydration, cation siting, cation type, or temperature-pressure conditions. By varying the level of distortion of double eight-rings, it is possible to control the adsorption properties, which confer a molecular valve behavior to this material. We have employed interatomic potentials-based simulations to obtain a detailed atomistic view of the structural distortion mechanisms of zeolite RHO, in contrast with the averaged and space group restricted information provided by diffraction studies. We have modeled four aluminosilicate structures, containing Li$^+$, Na$^+$, K$^+$, Ca$^{2+}$, and Sr$^{2+}$ cations. The distortions of the three different zeolite rings are coupled, and the six- and eight-membered rings are largely flexible. A large dependence on the polarizing power of the extra-framework cations and with the loading of water has been found for the minimum aperture of the eight-membered rings that control the nanovalve effect. The calculated energy barriers for moving the cations across the eight-membered rings are very high, which explains the experimentally observed slow kinetics of the phase transition as well as the appearance of metastable phases.

cond-mat.mtrl-sci↗

arXiv2015

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight.

cond-mat.mtrl-sci↗