# New tools for the systematic analysis and visualization of electronic excitations. I. Formalism

## Abstract

A variety of density matrix based methods for the analysis and visualization of electronic excitations are discussed and their implementation within the framework of the algebraic diagrammatic construction of the polarization propagator is reported. Their mathematical expressions are given and an extensive phenomenological discussion is provided to aid the interpretation of the results. Starting from several standard procedures, e.g., population analysis, natural orbital decomposition, and density plotting, we proceed to more advanced concepts of natural transition orbitals and attachment/detachment densities. In addition, special focus is laid on information coded in the transition density matrix and its phenomenological analysis in terms of an electron-hole picture. Taking advantage of both the orbital and real space representations of the density matrices, the physical information in these analysis methods is outlined, and similarities and differences between the approaches are highlighted. Moreover, new analysis tools for excited states are introduced including state averaged natural transition orbitals, which give a compact description of a number of states simultaneously, and natural difference orbitals (defined as the eigenvectors of the difference density matrix), which reveal details about orbital relaxation effects.

- Authors:

- Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)

- Publication Date:

- OSTI Identifier:
- 22308768

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DECOMPOSITION; DENSITY; DENSITY MATRIX; EIGENVECTORS; EXCITATION; EXCITED STATES; POLARIZATION

### Citation Formats

```
Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Wormit, Michael, and Dreuw, Andreas.
```*New tools for the systematic analysis and visualization of electronic excitations. I. Formalism*. United States: N. p., 2014.
Web. doi:10.1063/1.4885819.

```
Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Wormit, Michael, & Dreuw, Andreas.
```*New tools for the systematic analysis and visualization of electronic excitations. I. Formalism*. United States. doi:10.1063/1.4885819.

```
Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de, Wormit, Michael, and Dreuw, Andreas. Mon .
"New tools for the systematic analysis and visualization of electronic excitations. I. Formalism". United States.
doi:10.1063/1.4885819.
```

```
@article{osti_22308768,
```

title = {New tools for the systematic analysis and visualization of electronic excitations. I. Formalism},

author = {Plasser, Felix, E-mail: felix.plasser@iwr.uni-heidelberg.de and Wormit, Michael and Dreuw, Andreas},

abstractNote = {A variety of density matrix based methods for the analysis and visualization of electronic excitations are discussed and their implementation within the framework of the algebraic diagrammatic construction of the polarization propagator is reported. Their mathematical expressions are given and an extensive phenomenological discussion is provided to aid the interpretation of the results. Starting from several standard procedures, e.g., population analysis, natural orbital decomposition, and density plotting, we proceed to more advanced concepts of natural transition orbitals and attachment/detachment densities. In addition, special focus is laid on information coded in the transition density matrix and its phenomenological analysis in terms of an electron-hole picture. Taking advantage of both the orbital and real space representations of the density matrices, the physical information in these analysis methods is outlined, and similarities and differences between the approaches are highlighted. Moreover, new analysis tools for excited states are introduced including state averaged natural transition orbitals, which give a compact description of a number of states simultaneously, and natural difference orbitals (defined as the eigenvectors of the difference density matrix), which reveal details about orbital relaxation effects.},

doi = {10.1063/1.4885819},

journal = {Journal of Chemical Physics},

number = 2,

volume = 141,

place = {United States},

year = {Mon Jul 14 00:00:00 EDT 2014},

month = {Mon Jul 14 00:00:00 EDT 2014}

}