Real and Imaginary Excitons: Making Sense of Resonance Wave Functions by Using Reduced State and Transition Density Matrices

Within non-Hermitian quantum mechanics, metastable electronic states can be represented by isolated L-2-integrable complex-valued wave functions with complex energies. An analysis scheme of the real and imaginary parts of resonance wave functions by using reduced transition density matrices and natural transition orbitals is presented. While the real parts of excitons describe changes in the electron density corresponding to the bound part of the resonance, the imaginary excitons can be interpreted as virtual states facilitating one-electron decay into the continuum. The different nature of real and imaginary excitons is revealed by exciton descriptors, in particular hole-particle separation and their correlation. Singular values and respective participation ratios quantify the extent of collectivity of the excitation and a number of distinct decay channels. The utility of the new tool is illustrated by the analysis of bound and metastable excited states of cyanopolyyne anions.