Cebreiro-Gallardo Antonio, Casanova David
Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain.
Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia Saila, Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), PK 1072, 20080 Donostia, Euskadi, Spain.
Phys Chem Chem Phys. 2025 Apr 3;27(14):7093-7103. doi: 10.1039/d4cp04511d.
We present an efficient state-interaction approach for evaluating -shifts in high-spin molecular systems. Using a spin-orbit-coupled effective Hamiltonian with a restricted active space configuration interaction wavefunction, this method captures key excited-state contributions to -shifts without requiring large orbital spaces, maintaining computational efficiency. Additionally, we introduce a property-driven algorithm to automatically select relevant orbitals, optimizing the active space selection. Application to diatomic and conjugated organic molecules demonstrates accuracy comparable to advanced methods, providing detailed insight into the origins of -shifts. This methodology offers a flexible, efficient tool for exploring magnetic properties in complex molecules.
我们提出了一种用于评估高自旋分子体系中 - 位移的有效态相互作用方法。该方法使用具有受限活性空间组态相互作用波函数的自旋 - 轨道耦合有效哈密顿量，无需大的轨道空间就能捕捉到对 - 位移的关键激发态贡献，从而保持计算效率。此外，我们引入了一种属性驱动算法来自动选择相关轨道，优化活性空间的选择。将其应用于双原子和共轭有机分子，结果表明其准确性与先进方法相当，能深入了解 - 位移的起源。这种方法为探索复杂分子的磁性特性提供了一种灵活、高效的工具。
