Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Gymnasts and orienteers display better mental rotation performance than nonathletes

The aim of this study was to examine whether athletes differ from nonathletes regarding their mental rotation performance. Furthermore, it investigated whether athletes doing sports requiring distinguishable levels of mental rotation (orienteering, gymnastics, running), as well as varying with respect to having an egocentric (gymnastics) or an allocentric perspective (orienteering), differ from each other. Therefore, the Mental Rotations Test (MRT) was carried out with 20 orienteers, 20 gymnasts, 20 runners, and 20 nonathletes. The results indicate large differences in mental rotation performance, with those actively doing sports outperforming the nonathletes. Analyses for the specific groups showed that orienteers and gymnasts differed from the nonathletes, whereas endurance runners did not. Contrary to expectations, the mental rotation performance of gymnasts did not differ from that of orienteers. This study also revealed gender differences in favor of men. Implications regarding a differentiated view of the connection between specific sports and mental rotation performance are discussed.

Variability of mesospheric water vapor above Bern in relation to the 27-day solar rotation cycle

Many studies investigated solar–terrestrial responses (thermal state, O₃ , OH, H₂O) with emphasis on the tropical upper atmosphere. In this paper the Focus is switched to water vapor in the mesosphere at a mid-latitudinal location. Eight years of water vapor profile measurements above Bern (46.88°N/7.46°E) are investigated to study oscillations with the Focus on periods between 10 and 50 days. Different spectral analyses revealed prominent features in the 27-day oscillation band, which are enhanced in the upper mesosphere (above 0.1 hPa, ∼64 km) during the rising sun spot activity of solar cycle 24. Local as well as zonal mean Aura MLS observations Support these results by showing a similar behavior. The relationship between mesospheric water and the solar Lyman-α flux is studied by comparing thesi-milarity of their temporal oscillations. The H₂O oscillation is negatively correlated to solar Lyman-α oscillation with a correlation coefficient of up to −0.3 to −0.4, and the Phase lag is 6–10 days at 0.04 hPa. The confidence level of the correlation is ≥99%. This finding supports the assumption that the 27-day oscillation in Lyman-α causes a periodical photo dissociation loss in mesospheric water. Wavelet power spectra, cross-wavelet transform and wavelet coherence analysis (WTC)complete our study. More periods of high common wavelet power of H₂O and solar Lyman-α are present when amplitudes of the Lyman-α flux increase. Since this is not a measure of physical correlation a more detailed view on WTC is necessary, where significant (two sigma level)correlations occur intermittently in the 27 and 13-day band with variable Phase lock behavior. Large Lyman-α oscillations appeared after the solar super storm in July 2012 and the H₂O oscillations show a well pronounced anticorrelation. The competition between advective transport and photo dissociation loss of mesospheric water vapor may explain the sometimes variable Phase relationship of mesospheric H₂O and solar Lyman-α oscillations. Generally, the WTC analysis indicates that solar variability causes observable photochemical and dynamical processes in the mid-latitude mesosphere.

Insolation, erosion, and morphology of comet 67P/Churyumov-Gerasimenko

Context. The complex shape of comet 67P and its oblique rotation axis cause pronounced seasonal effects. Irradiation and hence activity vary strongly. Aims. We investigate the insolation of the cometary surface in order to predict the sublimation of water ice. The strongly varying erosion levels are correlated with the topography and morphology of the present cometary surface and its evolution. Methods. The insolation as a function of heliocentric distance and diurnal (spin dependent) variation is calculated using >10(5) facets of a detailed digital terrain model. Shading, but also illumination and thermal radiation by facets in the field of view of a specific facet are iteratively taken into account. We use a two-layer model of a thin porous dust cover above an icy surface to calculate the water sublimation, presuming steady state and a uniform surface. Our second model, which includes the history of warming and cooling due to thermal inertia, is restricted to a much simpler shape model but allows us to test various distributions of active areas. Results. Sublimation from a dirty ice surface yields maximum erosion. A thin dust cover of 50 pm yields similar rates at perihelion. Only about 6% of the surface needs to be active to match the observed water production rates at perihelion. A dust layer of 1 mm thickness suppresses the activity by a factor of 4 to 5. Erosion on the south side can reach more than 10 m per orbit at active spots. The energy input to the concave neck area (Hapi) during northern summer is enhanced by about 50% owing to self-illumination. Here surface temperatures reach maximum values along the foot of the Hathor wall. Integrated over the whole orbit this area receives the least energy input. Based on the detailed shape model, the simulations identify "hot spots" in depressions and larger pits in good correlation with observed dust activity. Three-quarters of the total sublimation is produced while the sub-solar latitude is south, resulting in a distinct dichotomy in activity and morphology. Conclusions. The northern areas display a much rougher morphology than what is seen on Imhotep, an area at the equator that will be fully illuminated when 67P is closer to the Sun. Self-illumination in concave regions enhance the energy input and hence erosion. This explains the early activity observed at Hapi. Cliffs are more prone to erosion than horizontal, often dust covered, areas, which leads to surface planation. Local activity can only persist if the forming cliff walls are eroding. Comet 67P has two lobes and also two distinct sides. Transport of material from the south to the north is probable. The morphology of the Imhotep plain should be typical for the terrains of the yet unseen southern hemisphere.