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Quantum mechanical treatment of variable molecular composition: from 'alchemical' changes of state functions to rational compound design

Chang, K. Y. Samuel and von Lilienfeld, O. Anatole. (2014) Quantum mechanical treatment of variable molecular composition: from 'alchemical' changes of state functions to rational compound design. Chimia, 68 (9). pp. 602-608.

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Abstract

'Alchemical' interpolation paths, i.e. coupling systems along fictitious paths without realistic correspondence, are frequently used within materials and molecular modeling simulation protocols for the estimation of changes in state functions such as free energies. We discuss alchemical changes in the context of quantum chemistry, and present illustrative numerical results for the changes of HOMO eigenvalue of the He atom due to alchemical teleportation - the simultaneous annihilation and creation of nuclear charges at different locations. To demonstrate the predictive power of alchemical first order derivatives (Hellmann-Feynman) the covalent bond potential of hydrogen fluoride and hydrogen chloride is investigated, as well as the hydrogen bond in the water-water and water-hydrogen fluoride dimer, respectively. Based on converged electron densities for one configuration, the versatility of alchemical derivatives is exemplified for the screening of entire binding potentials with reasonable accuracy. Finally, we discuss new constraints for the identification of non-linear coupling potentials for which the energy's Hellmann-Feynman derivative will yield accurate predictions.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Physikalische Chemie (Lilienfeld)
UniBasel Contributors:von Lilienfeld, Anatole
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Schweizerische Chemische Gesellschaft
ISSN:0009-4293
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:11 Jan 2017 14:31
Deposited On:20 Jun 2016 09:23

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