Hammett constants from density functional calculations: charge transfer and perturbations
Hammett constants from density functional calculations: charge transfer and perturbations
复制标题
密度泛函计算中的哈米特常数：电荷转移和扰动
DOI：
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发表时间：
2022
影响因子：
1.7
通讯作者：
R. Roy
中科院分区：
文献类型：
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作者：
R. Miranda‐Quintana;Nidhi Deswal;R. Roy
热力学和动力学组件的密度泛函反应性理论为基础的相互作用的电子受体和电子供体之间的稳定化能量进行评估，并不考虑由其他引起的一个反应物的微扰效应。通过这两种方法产生的两个能量分量的值然后与Hammett取代基常数$$left（σ）相关
八）$$ σ通过关系式$$sigma = mlog frac{{Delta E_{X}{{Delta E_{H}+ B$$ σ = mlog Δ E X Δ E H + B。这里$$Delta E_{X}$$ Δ E X和$$Delta E_{H}$$ Δ E H分别代表取代和未取代苯衍生物的能量组分（热力学或动力学）。六个不同系列的反应所产生的数据表明，微扰和非微扰的方法是可比的可靠性时，无论是热力学或动能组件中使用的建议的关系，证明的有效性和一般性的Hammett的自由能关系。
Thermodynamic and kinetic components of density functional reactivity theory -based stabilization energies between interacting electron acceptors and electron donors are evaluated with and without taking into account perturbative effects on one reactant caused by the other. The values of the two energy components generated through these two approaches are then correlated to the Hammett’s substituent constant $$left( sigma
ight)$$ σ through the relation $$sigma = mlog frac{{Delta E_{X} }}{{Delta E_{H} }} + b$$ σ = m log Δ E X Δ E H + b . Here $$Delta E_{X}$$ Δ E X and $$Delta E_{H}$$ Δ E H represent, respectively, energy components (either thermodynamic or kinetic) of the substituted and unsubstituted benzene derivatives. The generated data on six different series of reactions demonstrate that both perturbative and unperturbative approaches are of comparable reliability when either thermodynamic or kinetic energy components are used in the proposed relation, justifying the validity and generality of Hammett’s free energy relation.