DFT-Based ALMO-EDA

• Charge transfer (CT) in ALMO-EDA: stabilization effect due to inter-fragment orbital relaxation

• Perturbative charge-transfer analysis (CTA): decomposition of the amount of CT (ΔQ) and the associated energetic stabilization (ΔE) into forward and backward contributions

• Complementary occupied/virtual pairs (COVP) anaylsis

  • Based on perturbative CTA

  • Rotates the polarized ALMOs within a molecule to achieve a compact orbital representation of CT between a pair of molecules

  • Helps chemists quantify and visualize CT effects

• Variational forward-backward (VFB) analysis

  • Decomposes CT stabilization energy into forward and backward contributions using two variationally optimized “one-way” CT states

  • Can be seamlessly integrated with the adiabatic ALMO-EDA scheme, facilitating analysis of the effects of forward and backward CT on molecular properties