title: Monitoring conical intersections in the ring opening of furan by attosecond stimulated X-ray Raman spectroscopy.
abstract: Attosecond X-ray pulses are short enough to capture snapshots of molecules undergoing nonadiabatic electron and nuclear dynamics at conical intersections (CoIns). We show that a stimulated Raman probe induced by a combination of an attosecond and a femtosecond pulse has a unique temporal and spectral resolution for probing the nonadiabatic dynamics and detecting the ultrafast (∼4.5 fs) passage through a CoIn. This is demonstrated by a multiconfigurational self-consistent-field study of the dynamics and spectroscopy of the furan ring-opening reaction. Trajectories generated by surface hopping simulations were used to predict Attosecond Stimulated X-ray Raman Spectroscopy signals at reactant and product structures as well as representative snapshots along the conical intersection seam. The signals are highly sensitive to the changes in nonadiabatically coupled electronic structure and geometry.
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, USA.
authors.forename: Weijie
authors.initials: W
authors.lastname: Hua
authors.affiliation: Department of Chemistry, University of Munich , Butenandtstr. 5-13, D-81377 Munich, Germany.
authors.forename: Sven
authors.initials: S
authors.lastname: Oesterling
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, USA.
authors.forename: Jason D
authors.initials: JD
authors.lastname: Biggs
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, USA.
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, USA.
authors.forename: Hideo
authors.initials: H
authors.lastname: Ando
authors.affiliation: Department of Chemistry, University of Munich , Butenandtstr. 5-13, D-81377 Munich, Germany.
authors.forename: Regina
authors.initials: R
authors.lastname: de Vivie-Riedle
authors.forename: Benjamin P
authors.initials: BP
authors.lastname: Fingerhut
authors.affiliation: Department of Chemistry, University of California , Irvine, California 92697, USA.
authors.forename: Shaul
authors.initials: S
authors.lastname: Mukamel