Abstract
A 31-year-old letter from Professor Richard F. W. Bader to Professor Lou Massa outlining the connections between the quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT) especially with regard to the first Hohenberg-Kohn theorem is brought to light. This connection has not often been the topic of such a focused review by Bader and is presented here for the first time. The scientific importance of this letter is, in the opinion of the presenter, as timely today as it was back then in 1986. In Bader’s own opening words: “... that if I sent you a summary of what I think are the important connections between our work and density functional theory, ...”. He then takes us in a grand tour of the foundations of QTAIM culminating into the antecedents of a paper he later published with Professor Pierre Becker, whereby the Hohenberg-Kohn theorem is shown to operate at the level of an atom-in-a-molecule. Bader closes his letter by suggesting to Massa: “Study these two charge distributions – they are proof of the theorem of Hohenberg and Kohn”. By that Bader meant that when the charge distributions of two atoms or groups are identical within a given precision, then the kinetic and total energy contributions of these atoms to the corresponding molecular quantities are also identical. It is revealing to follow the intellectual threads weaved by Bader which provides us with a glimpse of his thought processes and intuition that guided him to some of his key discoveries. The lucidity, rigor, and clarity characteristic of Bader and the informality of style of a letter makes it of pedagogic and historic interest.
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Acknowledgements
The presenter thanks Professor Lou Massa for the careful reading of this manuscript and for approving its publication, Professor Tina Harriott (Mount Saint Vincent University) and Dr. Todd A. Keith (Semichem, Inc.) for their comments on the manuscript and helpful suggestions, and Ms. Carrie Armsworthy (Mount Saint Vincent University) for carefully transcribing the letter. Funding for this project was obtained from the Natural Sciences and Engineering Research Council of Canada (NSERC), Canada Foundation for Innovation (CFI), and Mount Saint Vincent University.
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This article is dedicated to Professor Lou Massa and to the memory of Professor Richard F. W. Bader.
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Matta, C.F. On the connections between the quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT): a letter from Richard F. W. Bader to Lou Massa. Struct Chem 28, 1591–1597 (2017). https://doi.org/10.1007/s11224-017-0946-7
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DOI: https://doi.org/10.1007/s11224-017-0946-7