Transient absorption (TA) is the most widespread method to follow ultrafast dynamics in molecules and materials. The related method of TA anisotropy (TAA) reports on the ultrafast reorientation dynamics of transition dipole moments, reporting on phenomena ranging from electronic dephasing to orientational diffusion. While these are fundamental aspects complementary to TA, TAA is generally less widely used. The main reason is that TAA signals are usually not measured directly but are retrieved from two consecutive TA measurements with parallel (R‖) and perpendicular (R⊥) polarization of pump and probe pulses. This means that even minor systematic errors in these measurements lead to drastic changes in the TAA signal. In this work, the authors demonstrate alternating shot-to-shot detection of R‖ and R⊥, minimizing systematic errors due to laser fluctuations. The employed broadband detection lets us discuss effects dependent on detection wavelength in the ultrafast anisotropy decay of 2,3-naphthalocyanine, a system previously scrutinized by David Jonas and co-workers. In particular, we compare timescales of population relaxation and decoherence and support the proposals for isotropic type of relaxation in square symmetric molecules.

Institute of Physics Faculty of Mathematics and Physics Charles University Prague 12116 Czechia

Technical University of Munich TUM School of Natural Sciences Department of Chemistry Professorship of Dynamic Spectroscopy 85748 Garching Germany

WSL Institut für Schnee und Lawinenforschung SLF 7260 Davos Dorf Switzerland

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