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Updated: Oct 27, 2025

Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
Published on: May 29, 2018
Threshold Photoelectron Spectrum of Cyclobutadiene: Comparison with Time-Dependent Wavepacket Simulations
Lea Bosse1, Barry P Mant2, Domenik Schleier1
1Institute of Physical and Theoretical Chemistry, University of Würzburg, D-97074 Würzburg, Germany.
Abstract:
The C4H4 isomer cyclobutadiene (CBD) is the prime model for antiaromaticity and thus a molecule of considerable interest in chemistry. Because it is highly reactive, it can only be studied under isolated conditions. Its electronic structure is characterized by a pseudo-Jahn-Teller effect in the neutral and a E ⊗ β Jahn-Teller effect in the cation. As a result, recording photoelectron spectra as well as describing them theoretically has been challenging. Here we present the photoion mass-selected threshold photoelectron spectrum of cyclobutadiene together with a simulation based on time-dependent wavepacket dynamics that includes vibronic coupling in the ion, taking into account eight vibrational modes in the cation. Excellent agreement between theory and experiment is found, and the ionization energy is revised to 8.06 ± 0.02 eV.
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