Showing papers by "Juergen Eckert published in 2014"

Simulations of hydrogen sorption in rht-MOF-1: Identifying the binding sites through explicit polarization and quantum rotation calculations

Abstract: Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in rht-MOF-1, a metal–organic framework (MOF) that consists of isophthalate groups joined by copper paddlewheel clusters and Cu3O trimers through tetrazolate moeities. This is a charged rht-MOF that contains extra-framework nitrate counterions within the material. For the simulations performed herein, excellent agreement with experiment was achieved for the simulated hydrogen sorption isotherms and calculated isosteric heat of adsorption, Qst, values only when using a polarizable potential. Thermodynamic agreement is demonstrated via comparing to experimental isotherms and binding sites are revealed by combining simulation and inelastic neutron scattering (INS) data. Simulations involving explicit many-body polarization interactions assisted in the determination of the binding sites in rht-MOF-1 through the distribution of the induced dipoles that led to strong adsorbate interactions. Four distinct hydrogen sorption sites were determined from the polarization distribution: the nitrate ions located in the corners of the truncated tetrahedral cages, the Cu2+ ions of the paddlewheels that project into the truncated tetrahedral and truncated octahedral cages (Cu1 ions), the Cu2+ ions of the Cu3O trimers (Cu3 ions), and the sides of the paddlewheels in the cuboctahedral cage. The simulations revealed that the initial sorption sites for hydrogen in rht-MOF-1 are the nitrate ions; this site corresponds to the high initial Qst value for hydrogen (9.5 kJ mol−1) in the MOF. The radial distribution functions, g(r), about the Cu2+ ions at various loadings revealed that the Cu1 ions are the preferred open-metal sorption sites for hydrogen at low loading, while the Cu3 ions become occupied at higher loadings. The validation of the aforementioned sorption sites in rht-MOF-1 was confirmed by calculating the two-dimensional quantum rotational levels about each site and comparing the levels to the transitions that were observed in the experimental INS spectra for hydrogen in the compound. For each binding site, the rotational transitions from j = 0 to j = 1 were in good agreement to certain transitions that were observed in the INS spectra. From these calculations, the assignment of the peaks in the INS spectra for hydrogen in rht-MOF-1 has been made.

Investigating the Gas Sorption Mechanism in an rht-Metal–Organic Framework through Computational Studies

Abstract: Grand canonical Monte Carlo (GCMC) simulations were performed to investigate CO2 and H2 sorption in an rht-metal–organic framework (MOF) that was synthesized with a ligand having a nitrogen-rich trigonal core through trisubstituted triazine groups and amine functional groups. This MOF was synthesized by two different groups, each reporting their own distinct gas sorption measurements and crystal structure. Electronic structure calculations demonstrated that the small differences in the atomic positions between each group’s crystal structure resulted in different electrostatic parameters about the Cu2+ ions for the respective unit cells. Simulations of CO2 sorption were performed with and without many-body polarization effects and using our recently developed CO2 potentials, in addition to a well-known bulk CO2 model, in both crystallographic unit cells. Simulated CO2 sorption isotherms and calculated isosteric heats of adsorption, Qst, values were in excellent agreement with the results reported previousl...

Capturing the H2–Metal Interaction in Mg-MOF-74 Using Classical Polarization

Abstract: Grand canonical Monte Carlo (GCMC) simulations of H2 sorption were performed in Mg-MOF-74, a metal–organic framework (MOF) that displays very high H2 sorption affinity. Experimental H2 sorption isotherms and isosteric heats of adsorption (Qst) values were reproduced using a general purpose materials sorption potential that includes many-body polarization interactions. In contrast, using two models that include only charge–quadrupole interactions failed to reproduce such experimental measurements even though they are the type normally employed in such classical force field calculations. Utilizing the present explicit polarizable model in GCMC simulation resulted in a Mg2+–H2 distance of 2.60 A, which is close to a previously reported value that was obtained using electronic structure methods and comparable to similar experimental measurements. The induced dipole distribution obtained from simulation assisted in the characterization of two previously identified sorption sites in the MOF: the Mg2+ ions and t...

Polymorphism of paracetamol: a new understanding of molecular flexibility through local methyl dynamics.

Abstract: This study focuses on the interplay of molecular flexibility and hydrogen bonding manifested in the monoclinic (form I) and orthorhombic (form II) polymorphs of paracetamol. By means of incoherent inelastic neutron scattering and density functional theory calculations, the relaxation processes related to the methyl side-group reorientation were analyzed in detail. Our computational study demonstrates the importance of considering quantum effects to explain how methyl reorientations and subtle conformational changes of the molecule are intertwined. Indeed, by analyzing the quasi elastic signal of the neutron data, we were able to show a unique and complex motional flexibility in form II, reflected by a coupling between the methyl and the phenyl reorientation. This is associated with a higher energy barrier of the methyl rotation and a lower Gibbs free energy when compared to form I. We put forward the idea that correlating solubility and molecular flexibility, through the relation between pKa and methyl ro...

Dramatic effect of pore size reduction on the dynamics of hydrogen adsorbed in metal–organic materials

Abstract: The effects of pore size reduction on the dynamics of hydrogen sorption in metal–organic materials (MOMs) were elucidated by studying SIFSIX-2-Cu and its doubly interpenetrated polymorph SIFSIX-2-Cu-i by means of sorption, inelastic neutron scattering (INS), and computational modeling. SIFSIX-2-Cu-i exhibits much smaller pore sizes, which possess high H2 sorption affinity at low loadings. Experimental H2 sorption measurements revealed that the isosteric heat of adsorption (Qst) for H2 in SIFSIX-2-Cu-i is nearly two times higher than that for SIFSIX-2-Cu (8.6 vs. 4.6 kJ mol−1). The INS spectrum for H2 in SIFSIX-2-Cu-i is rather unique for a porous material, as only one broad peak appears at low energies near 6 meV, which simply increases in intensity with loading until the pores are filled. The value for this rotational transition is lower than that in most neutral metal–organic frameworks (MOFs), including those with open Cu sites (8–9 meV), which is indicative of a higher barrier to rotation and stronger interaction in the channels of SIFSIX-2-Cu-i than the open Cu sites in MOFs. Simulations of H2 sorption in SIFSIX-2-Cu-i revealed two hydrogen sorption sites in the MOM: direct interaction with the equatorial fluorine atom (site 1) and between two equatorial fluorine atoms on opposite walls (site 2). The calculated rotational energy levels and rotational barriers for the two sites in SIFSIX-2-Cu-i are in good agreement with INS data. Furthermore, the rotational barriers and binding energies for site 2 are slightly higher than that for site 1, which is consistent with INS results. The lowest calculated transition for the primary site in SIFSIX-2-Cu is also in good agreement with INS data. In addition, this transition in the non-interpenetrating material is higher than any of the sites in SIFSIX-2-Cu-i, which indicates a significantly weaker interaction with the host as a result of the larger pore size.