Reconstructing ice-sheet accumulation rates at ridge B, East Antarctica

Understanding how ice sheets responded to past climate change is fundamental to forecasting how they will respond in the future. Numerical models calculating the evolution of ice sheets depend upon accumulation data, which are principally available from ice cores. Here, we calculate past rates of ice accumulation using internal layering. The englacial structure of the East Antarctic ice divide at ridge B is extracted from airborne ice-penetrating radar. The isochronous surfaces are dated at their intersection with the Vostok ice-core site, where the depth–age relationship is known. The dated isochrons are used as input to a one-dimensional ice-flow model to investigate the spatial accumulation distribution. The calculations show that ice-accumulation rates generally increase from Vostok lake towards ridge B. The western flank of the ice divide experiences markedly more accumulation than in the east. Further, ice accumulation increases northwards along the ice divide. The results also show the variability of accumulation in time and space around the ridge B ice divide over the last 124 000 years

Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (\u3c0\u3c0*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1\u20132 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (\u3c0\u3c3*) state, which is dissociative along the O\u2013H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.Peer reviewed: YesNRC publication: Ye

Excited electronic states of MnO4−:Challenges for wavefunction and density functional response theories

AbstractThe lowest excited electronic states of the permanganate ion MnO4− are calculated using a hierarchy of coupled cluster response approaches, as well as time-dependent density functional theory. It is shown that while full linear response coupled cluster with singles and doubles (or higher) performs well, that permanganate represents a stern test for approximate coupled cluster response models, and that problems can be traced to very large orbital relaxation effects. TD-DFT is reasonably robust although errors around 0.6eV are still observed. In order to further investigate the strong correlations prevalent in the electronic ground state large-scale RASSCF calculations were also performed. Again very large orbital relaxation in the correlated wavefunction is observed. Although the system can qualitatively be described by a single configuration, multi-reference diagnostic values show that care must be taken in this and similar metal complexes