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arXiv · 1610.04204

The particle-hole map: formal derivation and numerical implementation

Yonghui Li·Carsten A. Ullrich
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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 $\rm C_2H_4 - C_2F_4$.

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Yonghui Li, Carsten A. Ullrich. 2016-10-13. The particle-hole map: formal derivation and numerical implementation. https://doi.org/10.1063/1.4966036

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