Vibronic coherent quantum beat in four-layer platinum carbonyl cluster

Vibronic coherence has been studied for years, but direct comparisons between the rich experimental features and theory remain rare. In this work, we investigate the vibronic coherent quantum beat of a four-layer platinum carbonyl cluster [Pt3(CO)6]42- in a solution utilizing femtosecond vis-pump/vis-probe transient absorption spectroscopy. By varying the excitational wavelength, quantum beats coupled to either the electronic ground state or the excited state are selectively prepared. A 41 cm-1 beat at the ground state with a phase flip at 615 nm and a 28 cm-1 beat at the excited state with a phase node at 735 nm are observed. The beat amplitudes are asymmetric, stronger on the red side for ground state beats but weaker for excited state beats. Quantum chemistry calculations suggest that these beats result from coupling between the [Pt3(CO)6] layer motions and the electronic excitation. Theoretical model calculations for quantum beats at both electronic states are performed following the doorway-window approach. The calculations explain the oscillation frequency difference, the node positions, and the asymmetry. The beats with different frequencies result from vibronic coupling with different electronic states with the Herzberg-Teller (ground) or Franck-Condon term (excited) involved. The theoretical nodes occur at absorption and fluorescence centers, respectively, although experimental results show a slight blueshift. Quantum window operator calculations link the beat amplitude asymmetry to the Franck-Condon factor matrix imbalances, with the number of nodes dependent on the electronic dephasing rate. The theoretical insights for quantum beats are expected to be general, potentially helpful for the interpretation of observations in other systems.