The particle-hole map: formal derivation and numerical implementation

Abstract

The particle-hole map (PHM) is a tool to visualize electronic excitations, based on representations in a canonical orbital transition space. Introduced as an alternative to the transition density matrix, the PHM has a simple probabilistic interpretation, indicating the origins and destinations of electrons and holes and, hence, the roles of different functional units of molecules during an excitation. We present a formal derivation of the PHM, starting from the particle-hole transition density matrix and projecting onto a set of single-particle orbitals. We implement the PHM using atom-centered localized basis sets and discuss the example of the molecular charge-transfer complex ${\mathrm{C}}_2{\mathrm{H}}_4-{\mathrm{C}}_2{\mathrm{F}}_4$.

7 pages, 2 figures. To appear in J. Chem. Phys

References in corpus (2)

• Time-dependent electron localization function
• Quasi-particle spectra, absorption spectra, and excitonic properties of sodium iodide and strontium iodide from many-body perturbation theory

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