Rostock 2019 – scientific programme

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MO: Fachverband Molekülphysik

MO 4: Electronic Spectroscopy

MO 4.1: Invited Talk

Monday, March 11, 2019, 10:30–11:00, S HS 002 Biologie

Determination of Excited State Dipole Moments for Complex Systems - From Gas to the Condensed Phase — •Michael Schmitt, Marie-Luise Hebestreit, Mirko Lindic, Matthias Zajonz, and Michael Schneider — Heinreich-Heine-Universität, Insitut für Physikalische Chemie I, 40225 Düsseldorf, Germany

While in the gas phase, rotationally resolved electronic Stark spectroscopy is a versatile tool for the accurate determination of the permanent dipole moments in both states connected by the electronic transition, the situation in solution is less favorable. Although conceptionally simple and broadly applied, solvatochromic shifts for the determination of excited state dipole moments are inaccurate and lead sometimes to completely false results.

A variant, using thermochromic shifts, leads to more reliable results, but still has some pitfalls. On the other hand many molecules are thermally labile and cannot be brought into the gas phase without decomposition. In this contribution, we compare the values of excited state dipole moments from Stark spectroscopy with those from thermochromic shifts, and show some improvements to the method. The range of small (20 atoms) to large (more than 100 atoms) is covered, hereby.