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.

Being the lightest, most mobile atom that exists, hydrogen plays an important role in the chemistry of hydrocarbons, proteins and peptides and most biomolecules. Hydrogen can undergo transfer, exchange and migration processes, having considerable impact on the chemical behavior of these molecules. Although much has been learned about reaction dynamics involving one hydrogen atom, less is known about those processes where two or more hydrogen atoms participate. Here we show that single and double hydrogen migrations occurring in ethanol cations and dications take place within a few hundred fs to ps, using a 3D imaging and laser pump-probe technique. For double hydrogen migration, the hydrogens are not correlated, with the second hydrogen migration promoting the breakup of the C–O bond. The probability of double hydrogen migration is quite significant, suggesting that double hydrogen migration plays a more important role than generally assumed. The conclusions are supported by state-of-the-art molecular dynamics calculations.

a b s t r a c tThe LAPPD Collaboration was formed to develop ultrafast large-area imaging photodetectors based on new methods for fabricating microchannel plates (MCPs). In this paper we characterize the time response using a pulsed, sub-picosecond laser. We observe single-photoelectron time resolutions of a 20 cm  20 cm MCP consistently below 70 ps, spatial resolutions of roughly 500 μm, and median gains higher than 10 7 . The RMS measured at one particular point on an LAPPD detector is 58 ps, with 7 1σ of 47 ps. The differential time resolution between the signal reaching the two ends of the delay line anode is measured to be 5.1 ps for large signals, with an asymptotic limit falling below 2 ps as noise-over-signal approaches zero.

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