<> "The repository administrator has not yet configured an RDF license."^^ . <> . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials"^^ . "Graphene-based materials (GBMs) represent one of the most promising and sustainable alterna-\r\ntives to metal- and silicon-based systems in a plethora of practical applications, from sensing to\r\ncatalysis. However, the structural variability and lack of standard testing conditions make the\r\nefficient development of candidates for specific applications challenging. Nowadays, computational\r\nchemistry and materials science can aid experiments by providing crucial understanding of the be-\r\nhaviour of GBMs, but the choice of in silico models and theoretical methods is critical to achieve\r\nreliable and insightful results. Furthermore, compositional and structural variety and a broad\r\nrange of sizes of GBMs and their molecular (nano-) variants challenge the applicability of highly\r\naccurate ab initio methodologies. Clearly, better guidance is needed when deciding how to simulate\r\nthese functional organic materials accurately and efficiently.\r\nThe aim of this thesis is to address this need by studying how the choice of in silico model\r\nand of the level of theory influence computed properties of GBMs, from adsorption energetics to\r\nredox transformations. A large set of computational methods is employed, including semiempirical\r\ntight-binding, hybrid, and range-separated density functional theory in finite and periodic settings,\r\nsymmetry-adapted perturbation theory and many other wavefunction theory implementations, as\r\nwell as several energy and density decomposition approaches. The results are used to benchmark\r\nthe performance of these methods, formulate the guidelines for the best-practice techniques, un-\r\nderstand the chemical behaviour of the GBMs, and, ultimately, distil the design principles for new\r\nand improved materials.\r\nThe results and discussion of this work are provided in three chapters:\r\n• In Chapter 3 we present an extensive benchmarking of diverse theoretical approaches for\r\nthe adsorption of carbon dioxide on pristine graphene across model sizes and derive a simple yet\r\npowerful extrapolation scheme for accurate estimates of the adsorption energies on infinite GBMs.\r\n• In Chapter 4 we present a study on nitroaromatic compounds adsorbed on diverse graphene-\r\nbased sensing materials, highlighting the relationship between computed properties and experimen-\r\ntally determined limits of detection, and analysing how the size-dependency of these properties\r\nvaries with the chemical nature of the adsorbent.\r\n• In Chapter 5 we transfer the established extrapolation scheme to the redox properties of\r\nGBMs, namely, ionisation energy, electron affinity, and redox potentials. Given complex electronic\r\nstructures of the systems involved, we probe the reliability of single-reference approaches. We also\r\nshow that, in contrast to adsorption energies, the size-dependencies of these properties are not\r\naffected by the material’s functionalisation.\r\nThis works illustrates that choosing an appropriate theoretical methodology for modelling the\r\nchemistry of graphene-based materials is defined by both the balance between cost and accuracy\r\nand by the questions the simulations aim to answer."^^ . "2024" . . . . . . . "Anna"^^ . "Piras"^^ . "Anna Piras"^^ . . . . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (PDF)"^^ . . . "Piras_Anna_PhD_thesis_08_02_2024.pdf"^^ . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (Other)"^^ . . . . . . "indexcodes.txt"^^ . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (Other)"^^ . . . . . . "lightbox.jpg"^^ . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (Other)"^^ . . . . . . "preview.jpg"^^ . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (Other)"^^ . . . . . . "medium.jpg"^^ . . . "Predicting Adsorbent and Electronic Properties of Graphene-Based Materials (Other)"^^ . . . . . . "small.jpg"^^ . . "HTML Summary of #34612 \n\nPredicting Adsorbent and Electronic Properties of Graphene-Based Materials\n\n" . "text/html" . . . "540 Chemie"@de . "540 Chemistry and allied sciences"@en . .