Affiliation:
1. Department of Chemistry Johannes Gutenberg University Mainz Duesbergweg 10–14 55128 Mainz Germany
2. Institut für Festkörpertheorie and Center for Multiscale Theory and Computation Westfälische Wilhelms-Universität Münster Wilhelm-Klemm-Str. 10 48149 Münster Germany
Abstract
AbstractThe chromium(III) complex [Cr(ddpd)2][BF4]3shows two spin‐flip emission bands in the near‐infrared spectral region. These bands shift bathochromically by −14.1 and −7.7 cm−1 kbar−1under hydrostatic pressure (Angew. Chem. Int. Ed.2018,57, 11069). The present study elucidates the structural changes of the chromium(III) cations under pressure using density functional theory with periodic boundary conditions and the resulting effects on the excited state energies using high‐level CASSCF‐NEVPT2 calculations. The differences of the bands in pressure sensitivity are traced back to a different orbital occupation of the intraconfigurational excited states.
Funder
Deutsche Forschungsgemeinschaft
Subject
Physical and Theoretical Chemistry,Atomic and Molecular Physics, and Optics