Issue 24, 2024

Electronic structure analysis and DFT benchmarking of Rydberg-type alkali-metal-crown ether, -cryptand, and -adamanzane complexes

Abstract

Density functional theory (DFT) and electron propagator theory (EPT) calculations were performed to study ground and excited electronic structures of alkali-metal (M) coordinated 9-crown-3, 24-crown-8, [2.1.1]cryptand, o-Me2-1.1.1, and 36Adamanzane complexes. Each complex bears an expanded electron in the periphery and occupies diffuse 1p-, 1d-, 1f-type molecular orbitals (or superatomic 1P, 1D, 1F orbitals) in excited electronic states. The calculated superatomic shell model of the M(9-crown-3)2 is 1S, 1P, 1D, 1F, 2S, 2P, 2D, 1G and it is held by all other complexes up to the studied 1F level. Due to the highly diffuse nature of the electron, the ionization energies of these complexes are significantly lower (1.6–2.0 eV) and hence these complexes belong to the superalkali category. The ab initio EPT ionization energy and the excitation energies of the Li(9-crown-3)2 were used to evaluate DFT errors associated with a series of exchange correlation functionals that span multiple rungs of Jacob's ladder (i.e., GGA, meta-GGA, global GGA hybrid, meta-GGA hybrid, range-separated hybrid, double-hybrid). Among these, the best performing functional is the range-separated hybrid CAM-B3LYP and the errors are within 6% of high-level ab initio EPT results. The accuracy of CAM-B3LYP is indeed transferable to similar complexes and hence the findings are expected to accelerate the progression of studies of Rydberg-type systems.

Graphical abstract: Electronic structure analysis and DFT benchmarking of Rydberg-type alkali-metal-crown ether, -cryptand, and -adamanzane complexes

Supplementary files

Article information

Article type
Paper
Submitted
19 Feb 2024
Accepted
15 Apr 2024
First published
22 Apr 2024

Phys. Chem. Chem. Phys., 2024,26, 16989-16997

Electronic structure analysis and DFT benchmarking of Rydberg-type alkali-metal-crown ether, -cryptand, and -adamanzane complexes

I. R. Ariyarathna, Phys. Chem. Chem. Phys., 2024, 26, 16989 DOI: 10.1039/D4CP00723A

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