Substantial Errors from Time‐Dependent Density Functional Theory for the Calculation of Excited States of Large π Systems

作者：Stefan Grimme, Maja Parac · 发表于：ChemPhysChem · 年份：2003 · DOI：10.1002/cphc.200390047 · 被引用次数：510 · 研究领域：Advanced Chemical Physics Studies、Spectroscopy and Quantum Chemical Studies、Molecular spectroscopy and chirality

A warning to TDDFT users: Unexpected failures of the popular time-dependent DFT (TDDFT) method for the π→π* excited states (see figure) of large aromatic molecules are reported. A very probable reason for this behaviour is the underestimated interaction of important ionic components in the corresponding La-state wavefunctions with current standard functionals.