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<p>The inner reorganization energy of ten small molecule model systems was systematically assessed using 20 density functional approximations (DFA). All calculations were performed using the quantum chemistry software package ORCA. Experimental data were utilized to benchmark the DFAs when available; in instances where experimental values were absent, reorganization energies were computed using QD-NEVPT2/cc-pVTZ, using SC-NEVPT2 and FIC-NEVPT2 geometries. The results reveal that global-hybrid (GH) and meta-GGA global-hybrid (GH-mGGA) functionals with low exact exchange fraction (&lt; 0.25), as well as double hybrids (DH), provide reliable results for nonpolar systems. In contrast, range-separated hybrid (RSH) functionals and DH are more appropriate for systems exhibiting substantial charge localization. The IP tuning process enhanced the accuracy of the ωB97X-3c functional. Nonetheless, its effect was more significant in systems characterized by substantial electron delocalization. DH functionals exhibited superior adaptability among density functional approximations. The computation of reorganization energy for 4-boranylbuta-1,3-dien-1-amine (RBH<sub>2</sub>) faces challenges; inaccuracies in modeling C–B bond rotation in the cation resulted in overestimated reorganization energy for the neutral species. An analogous phenomenon has been identified for 1-N,1-N,4-N,4-N-tetramethylbenzene-1,4-diamine (TL85), where the localization of the nearly degenerate geometries (C<sub>s</sub>, C<sub>2</sub>, C<sub>2h</sub>, and C<sub>2v</sub>) is dependent upon the selected functional.</p>

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A comparative assessment of density functional approximations for inner reorganization energy: insights from small molecules models with varying degrees of charge delocalization

  • 期刊论文

  • 发表日期：

    2025年5月16日

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  • Raul Flores,
  • Nora Aydeé Sánchez-Bojorge,
  • Juan Pedro Palomares-Báez,
  • Linda-Lucila Landeros-Martínez,
  • Luz María Rodríguez-Valdez

摘要

The inner reorganization energy of ten small molecule model systems was systematically assessed using 20 density functional approximations (DFA). All calculations were performed using the quantum chemistry software package ORCA. Experimental data were utilized to benchmark the DFAs when available; in instances where experimental values were absent, reorganization energies were computed using QD-NEVPT2/cc-pVTZ, using SC-NEVPT2 and FIC-NEVPT2 geometries. The results reveal that global-hybrid (GH) and meta-GGA global-hybrid (GH-mGGA) functionals with low exact exchange fraction (< 0.25), as well as double hybrids (DH), provide reliable results for nonpolar systems. In contrast, range-separated hybrid (RSH) functionals and DH are more appropriate for systems exhibiting substantial charge localization. The IP tuning process enhanced the accuracy of the ωB97X-3c functional. Nonetheless, its effect was more significant in systems characterized by substantial electron delocalization. DH functionals exhibited superior adaptability among density functional approximations. The computation of reorganization energy for 4-boranylbuta-1,3-dien-1-amine (RBH2) faces challenges; inaccuracies in modeling C–B bond rotation in the cation resulted in overestimated reorganization energy for the neutral species. An analogous phenomenon has been identified for 1-N,1-N,4-N,4-N-tetramethylbenzene-1,4-diamine (TL85), where the localization of the nearly degenerate geometries (Cs, C2, C2h, and C2v) is dependent upon the selected functional.