Fractional Charge Density Functional Theory and Its Application to the Electro-inductive Effect

• DOI: 10.1021/acs.jpclett.3c00323
• Publication Date: 2023-03-29T21:24:05Z
• Authors: Jun-Hyeong Kim; Dongju Kim; Weitao Yang; Mu-Hyun Baik
• Keywords: 0103 physical sciences; 01 natural sciences

We employed the chemical potential neutralization principle to demonstrate that fractional electrons are involved in the electro-inductive effect as well as the vibrational Stark effect. By the chemical potential model, we were able to deduce that the frontier molecular orbitals of immobilized molecules can provide valuable insight into these effects. To further understand and quantify these findings, we introduced fractional charge density functional theory (FC-DFT), a canonical ensemble approach for open systems. This method allows for the calculation of electronic energies, nuclear gradients, and the Hessian matrix of fractional electronic systems. To correct the spurious delocalization error commonly found in approximate density functionals for small systems, we imposed the Perdew-Parr-Levy-Balduz (PPLB) condition through linear interpolation of two adjacent integer points (LI-FC-DFT). Although this approach is relatively simple in terms of molecular modeling, the results obtained through LI-FC-DFT calculations predict the same trend seen in experimental reactivity and the frequency change of immobilized molecules.