Exploring Chemical Space with the Alchemical Derivatives

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• 作者：Robert Balawender ; Meressa A. Welearegay ; Micha艂 Lesiuk ; Frank De Proft ; Paul Geerlings
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：December 10, 2013
• 年：2013
• 卷：9
• 期：12
• 页码：5327-5340
• 全文大小：511K
• 年卷期：v.9,no.12(December 10, 2013)
• ISSN：1549-9626

文摘

In this paper, we verify the usefulness of the alchemical derivatives in the prediction of chemical properties. We concentrate on the stability of the transmutation products, where the term 鈥渢ransmutation鈥?means the change of the nuclear charge at an atomic site at constant number of electrons. As illustrative transmutations showing the potential of the method in exploring chemical space, we present some examples of increasing complexity starting with the deprotonation, continuing with the transmutation of the nitrogen molecule, and ending with the substitution of isoelectronic B鈥揘 units for C鈥揅 units and N units for C鈥揌 units in carbocyclic systems. The basis set influence on the qualitative and quantitative accuracies of the alchemical predictions was investigated. The alchemical deprotonation energy (from the second order Taylor expansion) correlates well with the vertical deprotonation energy and can be used as a preliminary indicator for the experimental deprotonation energy. The results of calculations for the BN derivatives of benzene and pyrene show that this method has great potential for efficient and accurate scanning of chemical space.