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Simulating Transient Absorption Spectra using Extremely Broad X-ray Pulses
American Chemical Society Meeting
  • Anthony D. Dutoi, University of the Pacific
  • Stephen R. Leone, Lawrence Berkeley National Laboratory
Document Type
American Chemical Society (ACS)
San Francisco, CA
Conference Dates
August 10-14, 2014
Date of Presentation
Extremely short (less than 1 fs) soft x-ray pulses are emerging as cutting-edge tools for investigating molecules on time scales shorter than the oscillation of a chemical bond. The very large photon energies and band widths of such pulses pose serious challenges for ab initio simulations of transient x-ray absorption spectra because the relevant final molecular states are so high in energy (and are generally decaying), and because so many states will participate. We build a theoretical framework, within which electronically correlated computations can be used to understand the x-ray absorption spectra of vibrating molecules, resolved both spectrally and in time. In particular, absorption at core–valence resonances are computed as a function of the stretch coordinate for halogen molecules and their molecular ions. This yields insight into what spectral features can be expected when an x-ray probe is used to follow vibrational dynamics in real time. In experiments with Br2, strong-field ionization has already been seen to produce coherent stretching oscillations of both the molecular ion and the depleted neutral species. Foremostly, detailed understanding of the dominant transitions that contribute to such a spectrum is desired (their character, intensity, line shape, and dependence on the vibrational coordinate). This study lays the foundation for eventual convergence of combined experimental and theoretical study of a common system.
Citation Information
Anthony D. Dutoi and Stephen R. Leone. "Simulating Transient Absorption Spectra using Extremely Broad X-ray Pulses" American Chemical Society Meeting (2014)
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