Projects per year
Abstract
The diradical and ionic natures of open-shell singlet systems have been investigated using new definitions of the diradical and ionic characters as well as of their densities within the valence configuration interaction (VCI) model with two electrons in two active orbitals. The two-site symmetric and asymmetric diradical models are examined by using these diradical/ionic characters. For realistic compounds, we investigate a diradicaloid diphenalenyl and a rectangular graphene nanoflake in the presence of an external static electric field, as well as π-stacked phenalenyl-derivative dimers with varying the intermonomer distance, where the central carbon atoms in the phenalenyl rings are substituted by boron (B) and nitrogen (N) atoms, respectively. It is found that the increase of charge asymmetricity induced by the static electric field decreases the diradical character and finally induces an ionic character in the ground state, while the first excited state is changed from pure ionic to diradical-dominant as the field amplitude increases. On the other hand, when increasing the intermonomer distance, the B/N substitution in the phenalenyl dimer changes the electronic state from open-shell singlet with small diradical character to closed-shell with large ionic character. These results indicate that the application of a static electric field to diradicaloids and the asymmetric substitution of a pancake bonded π-dimer combined with the variation of intermonomer distance could tune the diradical/ionic characters and therefore control the nonlinear optical responses.
Original language | English |
---|---|
Pages (from-to) | 861-873 |
Number of pages | 13 |
Journal | The Journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
Volume | 121 |
Issue number | 4 |
DOIs | |
Publication status | Published - 2017 |
Keywords
- open-shell molecular systems
- Quantum chemistry
Fingerprint
Dive into the research topics of 'Diradical and Ionic Characters of Open-Shell Singlet Molecular Systems'. Together they form a unique fingerprint.Projects
- 3 Finished
-
Quantum chemical design of open-shell nonlinear optical materials
CHAMPAGNE, B. (PI), SEIDLER, T. (PI), DE WERGIFOSSE, M. (PI) & Nakano, M. (PI)
1/04/14 → 31/12/21
Project: Research
-
Functional Supramolecular Systems (IUAP No. P7/5) – Modeling the nonlinear optical properties of functionalized surfaced and complex systems
NENON, S. (PI) & CHAMPAGNE, B. (CoI)
1/06/12 → 31/12/13
Project: PHD
-
Equipment
-
High Performance Computing Technology Platform
Champagne, B. (Manager)
Technological Platform High Performance ComputingFacility/equipment: Technological Platform