Progress toward a one-electron model for the non-valence correlation-bound anions of polycyclic aromatic hydrocarbons
Progress toward a one-electron model for the non-valence correlation-bound anions of polycyclic aromatic hydrocarbons
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DOI：
10.1088/2516-1075/ac522a
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发表时间：
2022-03-01
影响因子：
2.6
通讯作者：
Jordan, Kenneth D.
中科院分区：
文献类型：
--
作者：
Mulvey, Devin M.;Jordan, Kenneth D.
用单电子模型哈密顿量表征了六方多环芳烃C6 n2 H6 n（n = 3-7）的非价相关束缚阴离子.该模型采用原子静电矩的四极，耦合诱导电荷和偶极子，和原子为中心的排斥高斯描述多余的电子和PAH之间的相互作用。这些模型组件的参数化和验证对全电子计算。从该模型得到的静态偶极极化率与PBE 0密度泛函理论和二阶M ø ller-Plesset微扰理论计算的结果吻合较好。在该模型中，电荷流占主导地位的面内极化率大于C54 H18的多环芳烃，产生的平均极化率与碳原子数的近似二次标度。静电相互作用的列入减少了电子结合能为最大的多环芳烃考虑约20%，并从上方和下方的环系统的平面向周边的电荷分布的移位。静电和极化相互作用的分析提供了洞察定性趋势的电子结合能和电荷分布的最低能量NVCB阴离子。
A one-electron model Hamiltonian is used to characterize the non-valence correlation-bound (NVCB) anions of hexagonal polycyclic aromatic hydrocarbons (PAHs) C6n2H6n (n = 3-7). The model incorporates atomic electrostatic moments up to the quadrupole, coupled inducible charges and dipoles, and atom-centered repulsive Gaussians to describe the interaction between the excess electron and PAH. These model components are parameterized on and validated against all-electron calculations. Good agreement is found between the static dipole polarizabilities obtained from the model and those from PBE0 density functional theory and second-order M & oslash;ller-Plesset perturbation theory calculations. In the model, charge flow dominates the in-plane polarizability of PAHs larger than C54H18, yielding an approximately quadratic scaling of the mean polarizabilty with the number of carbon atoms. Inclusion of electrostatic interactions decreases the electron binding energies for the largest PAHs considered by about 20% and shift charge distribution from above and below the plane of the ring system toward the periphery. Analysis of the electrostatic and polarization interactions provides insight into qualitative trends in the electron binding energy and the charge distribution of the lowest energy NVCB anion.