Abstract
UV pump–extreme UV (XUV) probe femtosecond transient absorption spectroscopy is used to study the 268 nm induced photodissociation dynamics of bromoform (CHBr3). Core-to-valence transitions at the Br(3d) absorption edge (∼70 eV) provide an atomic scale perspective of the reaction, sensitive to changes in the local valence electronic structure, with ultrafast time resolution. The XUV spectra track how the singly occupied molecular orbitals of transient electronic states develop throughout the C–Br bond fission, eventually forming radical Br and CHBr2 products. Complementary ab initio calculations of XUV spectral fingerprints are performed for transient atomic arrangements obtained from sampling excited-state molecular dynamics simulations. C–Br fission along an approximately symmetrical reaction pathway leads to a continuous change of electronic orbital characters and atomic arrangements. Two timescales dominate changes in the transient absorption spectra, reflecting the different characteristic motions of the light C and H atoms and the heavy Br atoms. Within the first 40 fs, distortion from symmetry to form a quasiplanar CHBr2 by the displacement of the (light) CH moiety causes significant changes to the valence electronic structure. Displacement of the (heavy) Br atoms is delayed and requires up to ∼300 fs to form separate Br + CHBr2 products. We demonstrate that transitions between the valence-excited (initial) and valence + core-excited (final) state electronic configurations produced by XUV absorption are sensitive to the localization of valence orbitals during bond fission. The change in valence electron-core hole interaction provides a physical explanation for spectral shifts during the process of bond cleavage.
Highlights
Photochemical reactions are the result of concerted electronicnuclear motion induced by light-matter interaction
We provide a detailed discussion of the connections between changes in the transient absorption spectra and the orbitals involved in the transitions, providing deep insight into the coupled electronic-nuclear dynamics throughout the dissociation of CHBr3
The element-specific nature of inner-shell spectroscopy is used to monitor the evolution of the valence electron environment of the different Br atoms from a well-localized perspective
Summary
Photochemical reactions are the result of concerted electronicnuclear motion induced by light-matter interaction. Gaining a fundamental understanding of these coupled dynamics by combining ultrafast spectroscopy with first principles calculations is the driving force behind a fast growing field of research.[1,2] For example, the UV photochemistry of halogen-containing molecules involves ultrafast carbon-halogen bond cleavage, forming radical species that are short-lived and highly reactive. Direct detection of transient species during the photoinduced dissociation of bromoform using core-to-valence transitions is demonstrated, which provides a sensitive probe of the evolving molecular electronic structure and nuclear geometry, with ultrafast time resolution. The photochemistry of halogen-containing species has significant practical implications.[3] For instance, bromoform is recognized as a key contributor to polar ozone depletion[4] and is the largest source of bromine in the atmosphere due to a combination of increased absorption at Struct.
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