We propose a scheme for probing the structure of vibrating molecules with photoelectrons generated from ultrashort soft-x-ray pulses. As an example we analyze below-100-eV photoelectrons liberated from the S(2p) orbital of vibrating SF₆ molecules to image very small structural changes of molecular vibration. In particular, photoionization cross sections and photoelectron angular distributions (PAD) at nonequilibrium geometries can be retrieved accurately with photoelectrons near the shape resonance at 13 eV. This is achieved with a pump-probe scheme, in which the symmetric stretch mode is first Raman excited predominantly by a relatively short laser pulse and then later probed at different time delays by a few-femtosecond soft-x-ray pulse with photon energy near 200 eV.



Keywords and Phrases

Molecules; Optical Pumping; Photoelectrons; Photoionization; Pumping (Laser); Sulfur Hexafluoride; Time Delay; Vibration Analysis, Non Equilibrium; Photoelectron Angular Distributions; Photoionization Cross Section; Pump-Probe Scheme; Shape Resonance; Short Laser Pulse; Soft X Ray Pulse; Vibrating Molecules, Photons

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Document Type

Article - Journal

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Final Version

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© 2016 American Physical Society (APS), All rights reserved.

Publication Date

01 Jun 2016

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Physics Commons