| 概 要 |
Since its development in the late 1950s and early 1960s [1,2], photoelectron spectroscopy has established itself as an important method to study the electronic structure of molecules, their photoionization dynamics, and the structure and dynamics of molecular cations. In recent years, and particularly since the development of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy [3], considerable progress has been made in the resolution that can be achieved by photoelectron spectroscopy. This progress relies on the systematic exploitation of the unusual physical properties of high Rydberg states and enables one today to resolve the rotational structure in the photoelectron spectrum of even large molecules.
This talk will begin with a brief historical review of photoelectron spectroscopy. Then, the relationship between photoelectron spectroscopy and the spectroscopy of high Rydberg states will be discussed in a systematic and pedagogical manner. It will be explained how this relationship is currently exploited to improve the resolution of PFI-ZEKE photoelectron spectroscopy. Then the physical principles that are at the heart of the latest methods related to photoelectron spectroscopy will be described together with their fundamental limitations. Depending on the resolution and the spectral range needed to address a specific scientific problem, several different methods can be used with spectral resolutions ranging from 30 GHz to better than 1 MHz [4-6].
The talk will summarize the current state-of-the-art in gas-phase photoelectron spectroscopy and be illustrated by several case studies, primarily taken from the research in my group, in which photoelectron spectroscopy has contributed to answer questions concerning the structure and dynamics of fundamental molecular cations.
[1] F. I. Vilesov, B. C. Kurbatov, and N. Terrenin, Soviet Phys. (Doklady) 6, 490 (1961)
[2] D. W. Turner and M. I. Al-Jobory, J. Chem. Phys. 37, 3007 (1962)
[3] G. Reiser, W. Habenicht, K. Muller-Dethlefs and E. W. Schlag, Chem. Phys. Lett. 152, 119 (1988)
[4] U. Hollenstein, R. Seiler, H. Schmutz, M. Andrist and F. Merkt, J. Chem. Phys. 115, 5461 (2001)
[5] R. Seiler, U. Hollenstein, G. Greetham and F. Merkt, Chem. Phys. Lett. 346, 201 (2001)
[6] A. Osterwalder, A. Wuest, Ch. Jungen and F. Merkt, J. Chem. Phys. 121, 11810 (2004)
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