How quantum-chemical geometry optimization level affects classical 3D descriptors and QSAR performance: a comparative study

量子化学几何优化水平如何影响经典三维描述符和QSAR性能:一项比较研究

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Abstract

Accurate representation of three-dimensional (3D) molecular structures is essential for quantitative structure-activity relationship (QSAR) modeling; however, it remains unclear whether increasing the level of theory used for quantum-chemical geometry optimization yields a practically meaningful benefit for classical conformation-dependent 3D descriptors (Dragon 3D) and the resulting QSAR performance. Here, we benchmark eight commonly used quantum-chemical (QM) geometry-optimization protocols-from minimal-basis Hartree-Fock (HF/STO-3 G) to def2-based hybrid density functional theory (DFT) and the composite method r 2 SCAN-3c-across three anticancer activity datasets and ten machine-learning classifiers. Descriptor-level analyses (relative deviation, rank correlation, and chemical-space similarity) reveal systematic method dependence in descriptor magnitudes: high-accuracy def2-based DFT protocols produce highly consistent descriptor spaces, whereas some intermediate/low-level settings introduce larger variability, although molecular rankings remain largely robust (Spearman ρ > 0.95 ). In contrast, downstream QSAR performance is only weakly affected by the QM level. Across paired dataset  ×  model blocks ( n = 30 ), mean balanced accuracies cluster tightly (0.852-0.871). B3LYP/3-21 G achieves the highest overall mean balanced accuracies (BA) (0.8709; 95% CI 0.8565-0.8840), while the lowest mean is observed for HF/STO-3 G (0.8518; 95% CI 0.8371-0.8661); def2-based B3LYP methods are numerically slightly lower (  ∼  0.855-0.856). A repeated-measures omnibus test indicates a statistically detectable method effect (Friedman p = 0.006 ) but with a small effect size (Kendall's W = 0.094 ), and post-hoc Wilcoxon tests with Holm correction identify only one robust pairwise difference (B3LYP/3-21 G vs. HF/STO-3 G, pHolm = 0.025 ). Thus, the observed performance shifts are marginal in magnitude (  ≤  1-2%) compared with the 10-100 ×  differences in computational cost.To support pragmatic method selection, we propose a two-tier Absolute Efficiency Ratio (AER) framework integrating predictive performance with efficiency and methodological considerations. Overall, these results indicate a non-linear and practically weak relationship between QM geometry-optimization level, classical 3D descriptor fidelity, and QSAR performance, suggesting that QM-level upgrades mainly reshape descriptor values without yielding commensurate or actionable gains in predictive accuracy.

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