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Pervasive Delocalisation Error Causes Spurious Proton Transfer in Organic Acid–Base Co‐Crystals
Author(s) -
LeBlanc Luc M.,
Dale Stephen G.,
Taylor Christopher R.,
Becke Axel D.,
Day Graeme M.,
Johnson Erin R.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201809381
Subject(s) - spurious relationship , protonation , density functional theory , proton , crystal (programming language) , base (topology) , benchmark (surveying) , chemistry , transfer (computing) , computational chemistry , materials science , chemical physics , computer science , physics , mathematics , ion , organic chemistry , quantum mechanics , machine learning , mathematical analysis , geodesy , parallel computing , programming language , geography
Abstract 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.