Lindgren Eric B
Departamento de Físico-Química, Instituto de Química, Universidade Federal Fluminense, 24020-141 Niterói, Rio de Janeiro, Brazil.
J Chem Theory Comput. 2025 Jun 24;21(12):6135-6150. doi: 10.1021/acs.jctc.5c00544. Epub 2025 Jun 12.
Electrostatic interactions in systems composed of finite-sized dielectric materials extend well beyond simple point-charge approximations, particularly when many-body polarization effects become significant. This study shows that asymmetries in the size or net charge of spherical particles can trigger nontrivial phenomena, including like-charge attraction and intricate force balances involving neutral species. Through a rigorous boundary-integral framework, it is substantiated that induced surface charges propagate through iterative cascades, reflecting the full many-body, nonadditive character of polarization. Significantly, a geometry-based cutoff is adopted to discriminate whether long-range interactions can be approximated by monopoles, thereby retaining near-field multipole couplings without forfeiting computational efficiency. This approach provides significant computational gains without compromising the rigor of many-body treatment, underscoring the critical interplay between geometric factors─specifically, particle size (and its associated curvature) and interparticle separation─in determining local field intensities, which often exceed conventional Coulombic predictions. The findings can illuminate pathways for understanding and designing advanced materials and self-assembled architectures in which dielectric polarization governs or contributes to emergent behavior.
由有限尺寸介电材料组成的系统中的静电相互作用远远超出了简单的点电荷近似，特别是当多体极化效应变得显著时。这项研究表明，球形粒子的尺寸或净电荷不对称会引发非平凡现象，包括同电荷吸引以及涉及中性物种的复杂力平衡。通过严格的边界积分框架，证实了感应表面电荷通过迭代级联传播，反映了极化的完整多体、非加性特征。值得注意的是，采用基于几何的截止来区分长程相互作用是否可以用单极子近似，从而在不牺牲计算效率的情况下保留近场多极耦合。这种方法在不损害多体处理严谨性的情况下提供了显著的计算优势，强调了几何因素（特别是粒子尺寸（及其相关曲率）和粒子间间距）在确定局部场强方面的关键相互作用，局部场强往往超过传统库仑预测。这些发现可以为理解和设计先进材料以及自组装结构提供途径，在这些材料和结构中，介电极化控制或促成了新出现的行为。
