Shungo Miyabe

Ultrafast X-ray Auger probing of photoexcited molecular dynamics

Molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation--X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C-O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.

Fragmentation pathways for selected electronic states of the acetylene dication

Coincident measurement of the Auger electron and fragment ion momenta emitted after carbon core-level photoionization of acetylene has yielded new understanding of how the dication fragments. Ab initio calculations and experimental data, including body-frame Auger angular distributions, are used to identify the parent electronic states and together yield a comprehensive map of the dissociation pathways which include surface crossings and barriers to direct dissociation. The Auger angular distributions for certain breakup channels show evidence of core–hole localization. (Some figures in this article are in colour only in the electronic version)

Probing ultrafast ππ* / nπ* internal conversion in organic chromophores via K-edge resonant absorption

Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons. Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state. The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure. Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy. As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance. We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs. High-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations.Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track. Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules.

Enhancement of strong-field multiple ionization in the vicinity of the conical intersection in 1,3-cyclohexadiene ring opening

Nonradiative energy dissipation in electronically excited polyatomic molecules proceeds through conical intersections, loci of degeneracy between electronic states. We observe a marked enhancement of laser-induced double ionization in the vicinity of a conical intersection during a non-radiative transition. We measured double ionization by detecting the kinetic energy of ions released by laser-induced strong-field fragmentation during the ring-opening transition between 1,3-cyclohexadiene and 1,3,5-hexatriene. The enhancement of the double ionization correlates with the conical intersection between the HOMO and LUMO orbitals.

Axis-dependence of molecular high harmonic emission in three dimensions

High-order harmonic generation in an atomic or molecular gas is a promising source of sub-femtosecond vacuum ultraviolet coherent radiation for transient scattering, absorption, metrology and imaging applications. High harmonic spectra are sensitive to Ångstrom-scale structure and motion of laser-driven molecules, but interference from radiation produced by random molecular orientations obscures this in all but the simplest cases, such as linear molecules. Here we show how to extract full body-frame high harmonic generation information for molecules with more complicated geometries by utilizing the methods of coherent transient rotational spectroscopy. To demonstrate this approach, we obtain the relative strength of harmonic emission along the three principal axes in the asymmetric-top sulphur dioxide. This greatly simplifies the analysis task of high harmonic spectroscopy and extends its usefulness to more complex molecules.

Experimental strategies for optical pump - soft x-ray probe experiments at the LCLS

Free electron laser (FEL) based x-ray sources show great promise for use in ultrafast molecular studies due to the short pulse durations and site/element sensitivity in this spectral range. However, the self amplified spontaneous emission (SASE) process mostly used in FELs is intrinsically noisy resulting in highly fluctuating beam parameters. Additionally timing synchronization of optical and FEL sources adds delay jitter in pump-probe experiments. We show how we mitigate the effects of source noise for the case of ultrafast molecular spectroscopy of the nucleobase thymine. Using binning and resorting techniques allows us to increase time and spectral resolution. In addition, choosing observables independent of noisy beam parameters enhances the signal fidelity.

Transient impulsive electronic Raman redistribution.

Resonant Raman excitation by ultrafast vacuum ultraviolet laser pulses is a powerful means to study electron dynamics in molecules, but experiments must contend with linear background ionization: frequencies high enough to reach resonant core-valence transitions will usually ionize all occupied orbitals as well, and the ionization cross sections are usually dominant. Here we show that attosecond pulses can induce a process, transient impulsive stimulated Raman scattering, which can overwhelm valence ionization. Calculations are performed for atomic sodium, but the principal is valid for many molecular systems. This approach opens the path for high-fidelity multidimensional spectroscopy with attosecond pulses.

Ultrafast X-ray probe of nucleobase photoprotection

We will present first results of a UV-pump X-ray-probe study of the photoprotection mechanism of thymine. The experiment used element specific Auger spectroscopy and was carried out at the LCLS.

Probing molecular photoinduced dynamics by ultrafast soft x-rays

Molecules selectively transform light energy from the sun into other forms of energy like heat, electricity, or chemical energy with high quantum efficiency. The energy conversion process is the result of a correlated motion of electrons and nuclei after photoexcitation, often under breakdown of the Born-Oppenheimer approximation. The element and site selectivity of x-rays allows observing molecular processes from a different point of view compared to ultrafast optical probes [1,2].

Delayed ultrafast X-ray induced auger probing

We present a new method for probing photoexcited molecular dynamics based on the site selective ionization via ultrafast x-rays followed by Auger decay.