Dispersion-corrected density-functional theory (DFT-D) methods have become the workhorse of many computational protocols for molecular crystal structure prediction due to their efficiency and convenience. However, certain limitations of DFT, such as delocalisation error, are often overlooked or are too expensive to remedy in solid-state applications. This error can lead to artificial stabilisation of charge transfer and, in this work, it is found to affect the correct identification of the protonation site in multicomponent acid-base crystals. As such, commonly used DFT-D methods cannot be applied with any reliability to the study of acid-base co-crystals or salts, while hybrid functionals remain too restrictive for routine use. This presents an impetus for the development of new functionals with reduced delocalisation error for solid-state applications; the structures studied herein constitute an excellent benchmark for this purpose.
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Density-functional theory models of Fe(iv)O reactivity in metal-organic frameworks: self-interaction error, spin delocalisation and the role of hybrid exchange.
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Institut de Ciència de Materials de Barcelona (ICMAB), Spanish National Research Council (CSIC), Campus de la UAB, Bellaterra, 08193, Spain.
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Angew Chem Int Ed Engl
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Department of Chemistry, Dalhousie University, P.O. Box 15000, 6274 Coburg Rd, Halifax, Nova Scotia, B3H 4R2, Canada.
Dispersion-corrected density-functional theory (DFT-D) methods have become the workhorse of many computational protocols for molecular crystal structure prediction due to their efficiency and convenience. However, certain limitations of DFT, such as delocalisation error, are often overlooked or are too expensive to remedy in solid-state applications. This error can lead to artificial stabilisation of charge transfer and, in this work, it is found to affect the correct identification of the protonation site in multicomponent acid-base crystals.
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