A New, Self-Contained Asymptotic Correction Scheme To Exchange-Correlation Potentials For Time-Dependent Density Functional Theory
By combining the asymptotic correction scheme of Casida and Salahub to exchange cor-relation potentials and the phenomenological linear correlation between experimental ionization potentials and highest occupied Kohn–Sham (KS) orbital energies found by Zhan, Nichols, and Dixon, we propose a new, expedient, and self-contained asymptotic correction to exchange-correlation potentials in KS density functional theory (DFT) for use in time-dependent density functional theory (TDDFT) that does not require an ionization potential as an external parameter from a separate calculation. The asymptotically-corrected (TD)DFT is implemented in the quan-tum chemistry program suite NWChem for both sequential and massively parallel execution. The method is shown to be well balanced for both valence- and Rydberg-type transitions with average errors in excitation energies of CO, N2, CH2O, and C2H4 being smaller than those of uncorrected BLYP and B3LYP TDDFT by a factor of 4 and 2, respectively. We demonstrate the general ap-plicability and accuracy of the method for the Rydberg excited states of mono- to tetra-fluorinated methanes, the valence and Rydberg excited states of benzene, and the Q, B, N, and L band posi-tions of free-base porphin.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 15010503
- Report Number(s):
- PNNL-SA-38880; 3530; KP1303000
- Journal Information:
- Journal of Physical Chemistry A, 107(10154-10158, Journal Name: Journal of Physical Chemistry A, 107(10154-10158
- Country of Publication:
- United States
- Language:
- English
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