The Particle-Hole Map: a Computational Tool to Visualize Electronic Excitations
14:15 - 15:15
Carsten A. Ullrich
University of Missouri, Columbia, USA
CFEL (Bldg. 99)
Seminar Room V, O1.109
The particle-hole map (PHM) is a new visualization tool to analyze electronic excitations in molecules in the time- or frequency domain, to be used in conjunction with TDDFT or other ab initio methods [1–3]. The purpose of the PHM is to give detailed insight into electronic excitation processes which is not obtainable from local visualization methods such as transition densities, density differences, or natural transition orbitals. The PHM provides information on the origins, destinations, and coherences of charge fluctuations during an excitation process. In contrast with the transition density matrix, the PHM has a statistical interpretation involving joint probabilities of individual states and their transitions, and it is easier to read and interpret.
We present a derivation of the PHM from the two-particle reduced
transition density matrix, discuss and illustrate its properties and
numerical implementation, and give several examples and applications to charge-transfer excitations in organic donor-acceptor systems.
This work was supported by NSF Grant No. DMR-1408904.
 Y. Li and C. A. Ullrich, J. Chem. Theory Comput. 11, 5838 (2015)
 Y. Li, D. Moghe, S. Patil, S. Guha, and C. A. Ullrich, Mol. Phys. 114, 1365 (2016)
 Y. Li and C. A. Ullrich, submitted to J. Chem. Phys. (2016)