DFT Screening on the Geometries and Electronic Properties of Organic Mixed-Valence Systems: Impact of Exchange-Correlation Functionals 


Vol. 69,  No. 2, pp. 53-66, Apr.  2025
10.5012/jkcs.2025.69.2.53


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  Abstract

This work evaluates the performance of 26 exchange-correlation functionals across three Robin-Day class II/III borderline organic mixed-valence (MV) systems (TBQ, HBQ, and DphD) focusing on geometries, redox potentials, IVCT excitation energies, and electronic couplings (H ). Calculated geometries demonstrated a tendency for most functionals to favor delocalized structures even for systems experimentally classified as class II or borderline class II/III. BMK-D3 exhibited most reliable performance of planar and linear systems but fails to reproduce π-stacked system. Global hybrid functionals with moderate exact exchange (27%–54%) provided superior redox potential predictions, with M06-D3 being the most reliable. Functionals with high exact exchange ( 54%) often predicted potential inversion, limiting their utility for MV systems. For IVCT excitation energies, low-to-moderate exact exchange (15–35%) functionals, such as M06-D3 and mPW1PW91, were most accurate. These findings highlight the importance of functional selection in modeling MV systems and position M06-D3 as a versatile choice for balancing accuracy across properties.

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  Cite this article

[IEEE Style]

K. C. Cho, J. H. Park, Y. K. Kang, "DFT Screening on the Geometries and Electronic Properties of Organic Mixed-Valence Systems: Impact of Exchange-Correlation Functionals," Journal of the Korean Chemical Society, vol. 69, no. 2, pp. 53-66, 2025. DOI: 10.5012/jkcs.2025.69.2.53.

[ACM Style]

Kyu Cheol Cho, Ji Hoon Park, and Youn K. Kang. 2025. DFT Screening on the Geometries and Electronic Properties of Organic Mixed-Valence Systems: Impact of Exchange-Correlation Functionals. Journal of the Korean Chemical Society, 69, 2, (2025), 53-66. DOI: 10.5012/jkcs.2025.69.2.53.

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ISSN(Print) 1017-2548
ISSN(Online) 2234-8530