Exploring Chemical Space with the Alchemical Derivatives
Exploring Chemical Space with the Alchemical Derivatives
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DOI：
10.1021/ct400706g
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发表时间：
2013-12-01
影响因子：
5.5
通讯作者：
Geerlings, Paul
中科院分区：
文献类型：
--
作者：
Balawender, Robert;Welearegay, Meressa A.;Geerlings, Paul
在本文中，我们验证了有用的炼金术衍生物的化学性质的预测。我们集中讨论嬗变产物的稳定性，这里的“嬗变”一词是指在恒定电子数的原子位置上核电荷的变化。作为展示该方法在探索化学空间中的潜力的说明性嬗变，我们提出了一些增加复杂性的例子，从去质子化开始，继续氮分子的嬗变，最后以等电子B-N单元取代碳环系统中的C-C单元和N单元取代C-H单元。研究了基组对炼金术预测的定性和定量准确性的影响。炼金术的去质子化能量（从二阶泰勒展开）相关以及与垂直去质子化能量，可以作为实验去质子化能量的初步指标。对苯和芘的BN衍生物的计算结果表明，该方法具有高效、准确的化学空间扫描潜力。
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 "transmutation" 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-N units for C-C units and N units for C-H 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.