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The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction
(2019)
The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.
In recent years, H/V measurements have been increasingly used to map the thickness of sediment fill in sedimentary basins in the context of seismic hazard assessment. This parameter is believed to be an important proxy for the site effects in sedimentary basins (e.g. in the Los Angeles basin). Here we present the results of a test using this approach across an active normal fault in a structurally well known situation. Measurements on a 50 km long profile with 1 km station spacing clearly show a change in the frequency of the fundamental peak of H/V ratios with increasing thickness of the sediment layer in the eastern part of the Lower Rhine Embayment. Subsequently, a section of 10 km length across the Erft-Sprung system, a normal fault with ca. 750 m vertical offset, was measured with a station distance of 100 m. Frequencies of the first and second peaks and the first trough in the H/V spectra are used in a simple resonance model to estimate depths of the bedrock. While the frequency of the first peak shows a large scatter for sediment depths larger than ca. 500 m, the frequency of the first trough follows the changing thickness of the sediments across the fault. The lateral resolution is in the range of the station distance of 100 m. A power law for the depth dependence of the S-wave velocity derived from down hole measurements in an earlier study [Budny, 1984] and power laws inverted from dispersion analysis of micro array measurements [Scherbaum et al., 2002] agree with the results from the H/V ratios of this study
To address one of the central questions of plate tectonics-How do large transform systems work and what are their typical features?-seismic investigations across the Dead Sea Transform (DST), the boundary between the African and Arabian plates in the Middle East, were conducted for the first time. A major component of these investigations was a combined reflection/ refraction survey across the territories of Palestine, Israel and Jordan. The main results of this study are: (1) The seismic basement is offset by 3-5 km under the DST, (2) The DST cuts through the entire crust, broadening in the lower crust, (3) Strong lower crustal reflectors are imaged only on one side of the DST, (4) The seismic velocity sections show a steady increase in the depth of the crust-mantle transition (Moho) from 26 km at the Mediterranean to 39 km under the Jordan highlands, with only a small but visible, asymmetric topography of the Moho under the DST. These observations can be linked to the left-lateral movement of 105 km of the two plates in the last 17 Myr, accompanied by strong deformation within a narrow zone cutting through the entire crust. Comparing the DST and the San Andreas Fault (SAF) system, a strong asymmetry in subhorizontal lower crustal reflectors and a deep reaching deformation zone both occur around the DST and the SAF. The fact that such lower crustal reflectors and deep deformation zones are observed in such different transform systems suggests that these structures are possibly fundamental features of large transform plate boundaries