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Issue 47, 2015
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Configuration interaction singles based on the real-space numerical grid method: Kohn–Sham versus Hartree–Fock orbitals

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Abstract

We developed a program code of configuration interaction singles (CIS) based on a numerical grid method. We used Kohn–Sham (KS) as well as Hartree–Fock (HF) orbitals as a reference configuration and Lagrange-sinc functions as a basis set. Our calculations show that KS-CIS is more cost-effective and more accurate than HF-CIS. The former is due to the fact that the non-local HF exchange potential greatly reduces the sparsity of the Hamiltonian matrix in grid-based methods. The latter is because the energy gaps between KS occupied and virtual orbitals are already closer to vertical excitation energies and thus KS-CIS needs small corrections, whereas HF results in much larger energy gaps and more diffuse virtual orbitals. KS-CIS using the Lagrange-sinc basis set also shows a better or a similar accuracy to smaller orbital space compared to the standard HF-CIS using Gaussian basis sets. In particular, KS orbitals from an exact exchange potential by the Krieger–Li–Iafrate approximation lead to more accurate excitation energies than those from conventional (semi-) local exchange–correlation potentials.

Graphical abstract: Configuration interaction singles based on the real-space numerical grid method: Kohn–Sham versus Hartree–Fock orbitals

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Publication details

The article was received on 20 Jan 2015, accepted on 31 Mar 2015 and first published on 01 Apr 2015


Article type: Paper
DOI: 10.1039/C5CP00352K
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Citation: Phys. Chem. Chem. Phys., 2015,17, 31434-31443
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    Configuration interaction singles based on the real-space numerical grid method: Kohn–Sham versus Hartree–Fock orbitals

    J. Kim, K. Hong, S. Choi, S. Hwang and W. Youn Kim, Phys. Chem. Chem. Phys., 2015, 17, 31434
    DOI: 10.1039/C5CP00352K

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