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

Type of content
Journal Article
Thesis discipline
Degree name
Publisher
AMER INST PHYSICS
Journal Title
Journal ISSN
Volume Title
Language
English
Date
2015
Authors
Lindoy LP
Kolmann SJ
D'Arcy JH
Jordan MJT
Crittenden, Deborah
Abstract

Finite temperature quantum and anharmonic effects are studied in H2-Li+-benzene, a model hydrogen storage material, using path integral Monte Carlo (PIMC) simulations on an interpolated potential energy surface refined over the eight intermolecular degrees of freedom based upon M05-2X/6-311+G(2df,p) density functional theory calculations. Rigid-body PIMC simulations are performed at temperatures ranging from 77 K to 150 K, producing both quantum and classical probability density histograms describing the adsorbed H2. 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 H2 molecule. The rigid-body PIMC simulations also provide estimates of the change in internal energy, ΔUads, and enthalpy, ΔHads, for H2 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 H2-Li+-benzene are the "helicopter" and "ferris wheel" H2 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 ΔUads and ΔHads are -13.3 ± 0.1 and -14.5 ± 0.1 kJ mol-1, respectively.

Description
Citation
Lindoy LP, Kolmann SJ, D'Arcy JH, Crittenden DL, Jordan MJT (2015). Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials. The Journal of Chemical Physics. 143(19).
Keywords
Science & Technology, Physical Sciences, Chemistry, Physical, Physics, Atomic, Molecular & Chemical, Chemistry, Physics, METAL-ORGANIC FRAMEWORKS, POTENTIAL-ENERGY SURFACES, MOLECULAR-ORBITAL METHODS, BASIS-SETS, ADSORPTION, INTERPOLATION, TEMPERATURE, MOF-177, SYSTEMS, SITES
Ngā upoko tukutuku/Māori subject headings
ANZSRC fields of research
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Fields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistry
Fields of Research::34 - Chemical sciences::3402 - Inorganic chemistry::340209 - Organometallic chemistry
Fields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340704 - Theoretical quantum chemistry
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