Multi-dimensional photoelectron spectroscopy of solvated molecules
Optics, Quantum Optics and Physics of Atoms, Molecules and Plasmas
Final Report Abstract
In summary, the results of this project established XUV time-resolved photoelectron spectroscopy as an analytical tool for investigation of electronic relaxation of organic molecules in solution. Photoelectron spectrosopy as a probe allows obtaining ionization energies of transient electronic states as the molecule relaxes through a series of conical intersections. The results were compared with high level state-of-the-art ab initio calculations, performed by collaborators, and allowed benchmarking of those calculations. In particular the combined investigation of relaxation dynamics of two amino-azobenzene molecules, Methyl Orange and Metanil Yellow, revealed the importance of the charge-transfer states in these molecules and, correspondingly, favored the use of the B3LYPD3 exchange functional over the WB97XD functional in these DFT-based studies. The investigation of the vertical ionization energies of the biomimetic switch molecules, NAIP and HDIOP, with opposite charges, confirm the importance of a detailes solvation model for proper description of their electronic structure. In the course of the implementation the project several important technical and scientific results have been achieved. It was shown that solubility of molecules typically negatively correlates to the signals observed in PES studies at liquid surfaces, which is important for the future choice of solutes and solvents for these types of investigations. Experiments, conducted in the commissioning phase of the XUV time-resolved photoelectron spectropscpy beamline also resulted in several important results in the gas phase spectroscopy, such as observation of the gross structure in NIR-assisted sideband generation and delayed electronic relaxation and grounds state intramolecular vibrational relaxation in naphthalene cations created by ionization with energetic XUV photons.
Publications
- “Femtosecond Extreme Ultraviolet Photoelectron Spectroscopy of Organic Molecules in Aqueous Solution”, J. Phys. Chem. Lett. 9, 22, 6649–6655 (2018)
J. Hummert, G. Reitsma, N. Mayer, E. Ikonnikov, M. Eckstein, and O. Kornilov
(See online at https://doi.org/10.1021/acs.jpclett.8b02937) - “Delayed relaxation of highly excited cationic states in naphthalene”, J. Phys. Chem. A 123 3068-3073 (2019)
G. Reitsma, J. Hummert, J. Dura, V. Loriot, M. J. J. Vrakking, F. Lepine, O. Kornilov
(See online at https://doi.org/10.1021/acs.jpca.8b10444) - “Timeresolved photoelectron spectroscopy of organic molecules in aqueous solutions”, EPJ Web Conf. 205, 09027 (2019)
J. Hummert, G. Reitsma, N. Mayer, E. Ikonnikov, M. Eckstein and Oleg Kornilov
(See online at https://doi.org/10.1051/epjconf/201920509027) - “Retrieving intracycle interference in angle-resolved laser-assisted photoemission from argon”, J. Phys. B: At., Mol. and Opt. Phys. 53, 154003 (2020)
J. Hummert, M. Kubin, S. López, J. I. Fuks, F. Morales, M. J. J. Vrakking, O. Kornilov, D. G. Arbo
(See online at https://doi.org/10.1088/1361-6455/ab94c9) - “Electronic relaxation of aqueous aminoazobenzenes studied by time-resolved photoelectron spectroscopy and surface hopping TDDFT dynamics calculations”, Faraday Discuss. 228, 226-241 (2021)
E. Titov, H. Hummert, E. Ikonnikov, R. Mitric, O. Kornilov
(See online at https://doi.org/10.1039/d0fd00111b) - “Femtosecond XUV-IR induced photodynamics in the methyl iodide cation”, New J. Phys. 23, 073023 (2021)
M. L. Murillo-Sanchez, G. Reitsma, S. Marggi Poullain, P. Fernández-Milán, J. Gonzalez- Vázquez, R. de Nalda, F. Martín, M. J. J. Vrakking, O. Kornilov, L. Banares
(See online at https://doi.org/10.1088/1367-2630/ac0c9b) - “Vibrational relaxation of XUV-induced hot ground state cations of Naphthalene”, J. Phys. Chem. A 125, 8549-8556 (2021)
G. Reitsma, S. Patchkovskii, J. Dura, L. Drescher, J. Mikosch, M. J. J. Vrakking, O. Kornilov
(See online at https://doi.org/10.1021/acs.jpca.1c05260)
