Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies

Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao; Yang, Weitao

doi:10.1080/00268976.2017.1382738

Cited by 10 publications

(17 citation statements)

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“…As already been pointed out in Zhang et al (2018), the use of a very diffuse basis set (such as aug-cc-pVTZ) may give rise to highly delocalized virtual KS/GKS orbitals with energies close to the molecular chemical potential. These orbitals are actually not relevant to the resonant state of the temporary anion of our interest, and should be left out of theoretical analysis.…”

Section: Resonance Energies Of Temporary Anionsmentioning

confidence: 95%

“…Alternatively, using the scaling corrected LUMO energy to determine the energy of the temporary anion has made impressive progress. It has been demonstrated that the GSC-PBE functional predicts highly accurate negative EAs by using Equation 16 (Zhang et al, 2018). For a set of 38 molecules proposed in Tozer and De Proft (2005), the resulting MAE is as small as 0.18 eV with the aug-cc-pVTZ basis set.…”

Section: Resonance Energies Of Temporary Anionsmentioning

confidence: 99%

“…An accurate prediction of molecular IP and EA has been achieved by employing the GSC approach (Zheng et al, 2013(Zheng et al, , 2015Zhang et al, 2015Zhang et al, , 2018…”

Section: Gsc Approach For the Accurate Prediction Of Ks/gks Orbital Ementioning

confidence: 99%

“…In order to describe the unbound resonance states within the DFT approach, Tozer and De Proft (2005) have proposed an approximate approach to evaluate the EA based on the KS frontier orbital energies (Kohn and Sham, 1965) and the accurate IP. Zhang et al (2018) have used directly the negative of GKS eigenvalue of the neutral ground-state molecule as an approximation of EA corresponding to the resonance state of the anion. The good accuracy was made possible because of the use of the global scaling correction (GSC) (Zheng et al, 2011), which will be introduced later.…”

Section: Introductionmentioning

confidence: 99%

“…Different from GSC, this method is designed to impose the derivative discontinuity of the exact XC potential. Our work (Zhang et al, 2018) proceeded the work of and that of Haiduke and Bartlett (Haiduke and Bartlett, 2018) in the direct use of GKS eigenvalues of the N-electron ground state to approximate the excited state energy of the corresponding (N + 1)-electron system, with the excited state of the (N + 1)-electron system being a unbound resonance state.…”

Section: Introductionmentioning

confidence: 99%

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Density Functional Prediction of Quasiparticle, Excitation, and Resonance Energies of Molecules With a Global Scaling Correction Approach

2020

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Molecular quasiparticle and excitation energies determine essentially the spectral characteristics measured in various spectroscopic experiments. Accurate prediction of these energies has been rather challenging for ground-state density functional methods, because the commonly adopted density function approximations suffer from delocalization error. In this work, by presuming a quantitative correspondence between the quasiparticle energies and the generalized Kohn–Sham orbital energies, and employing a previously developed global scaling correction approach, we achieve substantially improved prediction of molecular quasiparticle and excitation energies. In addition, we also extend our previous study on temporary anions in resonant states, which are associated with negative molecular electron affinities. The proposed approach does not require any explicit self-consistent field calculation on the excited-state species, and is thus highly efficient and convenient for practical purposes.

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Section: Resonance Energies Of Temporary Anionsmentioning

confidence: 95%

Section: Resonance Energies Of Temporary Anionsmentioning

confidence: 99%

“…An accurate prediction of molecular IP and EA has been achieved by employing the GSC approach (Zheng et al, 2013(Zheng et al, , 2015Zhang et al, 2015Zhang et al, , 2018…”

Section: Gsc Approach For the Accurate Prediction Of Ks/gks Orbital Ementioning

confidence: 99%