Time-resolved photoelectron spectroscopy of wavepackets through a conical intersection in NO_2

We report the results of theoretical studies of the time-resolved femtosecond photoelectron spectroscopy of quantum wavepackets through the conical intersection between the first two ^2A′ states of NO_2. The Hamiltonian explicitly includes the pump-pulse interaction, the nonadiabatic coupling due to the conical intersection between the neutral states, and the probe interaction between the neutral states and discretized photoelectron continua. Geometry- and energy-dependent photoionization matrix elements are explicitly incorporated in these studies. Photoelectron angular distributions are seen to provide a clearer picture of the ionization channels and underlying wavepacket dynamics around the conical intersection than energy-resolved spectra. Time-resolved photoelectron velocity map images are also presented

Modulation of Rab GTPase function by a protein phosphocholine transferase.

The intracellular pathogen Legionella pneumophila modulates the activity of host GTPases to direct the transport and assembly of the membrane-bound compartment in which it resides. In vitro studies have indicated that the Legionella protein DrrA post-translationally modifies the GTPase Rab1 by a process called AMPylation. Here we used mass spectrometry to investigate post-translational modifications to Rab1 that occur during infection of host cells by Legionella. Consistent with in vitro studies, DrrA-mediated AMPylation of a conserved tyrosine residue in the switch II region of Rab1 was detected during infection. In addition, a modification to an adjacent serine residue in Rab1 was discovered, which was independent of DrrA. The Legionella effector protein AnkX was required for this modification. Biochemical studies determined that AnkX directly mediates the covalent attachment of a phosphocholine moiety to Rab1. This phosphocholine transferase activity used CDP-choline as a substrate and required a conserved histidine residue located in the FIC domain of the AnkX protein. During infection, AnkX modified both Rab1 and Rab35, which explains how this protein modulates membrane transport through both the endocytic and exocytic pathways of the host cell. Thus, phosphocholination of Rab GTPases represents a mechanism by which bacterial FIC-domain-containing proteins can alter host-cell functions

Time-resolved photoelectron spectroscopy of proton transfer in the ground state of chloromalonaldehyde: Wave-packet dynamics on effective potential surfaces of reduced dimensionality

We report on a simple but widely useful method for obtaining time-independent potential surfaces of reduced dimensionality wherein the coupling between reaction and substrate modes is embedded by averaging over an ensemble of classical trajectories. While these classically averaged potentials with their reduced dimensionality should be useful whenever a separation between reaction and substrate modes is meaningful, their use brings about significant simplification in studies of time-resolved photoelectron spectra in polyatomic systems where full-dimensional studies of skeletal and photoelectron dynamics can be prohibitive. Here we report on the use of these effective potentials in the studies of dump-probe photoelectron spectra of intramolecular proton transfer in chloromalonaldehyde. In these applications the effective potentials should provide a more realistic description of proton-substrate couplings than the sudden or adiabatic approximations commonly employed in studies of proton transfer. The resulting time-dependent photoelectron signals, obtained here assuming a constant value of the photoelectron matrix element for ionization of the wave packet, are seen to track the proton transfer

Real-time observation of intramolecular proton transfer in the electronic ground state of chloromalonaldehyde: An ab initio study of time-resolved photoelectron spectra

The authors report on studies of time-resolved photoelectron spectra of intramolecular proton transfer in the ground state of chloromalonaldehyde, employing ab initio photoionization matrix elements and effective potential surfaces of reduced dimensionality, wherein the couplings of proton motion to the other molecular vibrational modes are embedded by averaging over classical trajectories. In the simulations, population is transferred from the vibrational ground state to vibrationally hot wave packets by pumping to an excited electronic state and dumping with a time-delayed pulse. These pump-dump-probe simulations demonstrate that the time-resolved photoelectron spectra track proton transfer in the electronic ground state well and, furthermore, that the geometry dependence of the matrix elements enhances the tracking compared with signals obtained with the Condon approximation. Photoelectron kinetic energy distributions arising from wave packets localized in different basins are also distinguishable and could be understood, as expected, on the basis of the strength of the optical couplings in different regions of the ground state potential surface and the Franck-Condon overlaps of the ground state wave packets with the vibrational eigenstates of the ion potential surface

Entropy of monopoles from percolating cluster in quenched SU(2) QCD

The length distribution and the monopole action of the infrared monopole clusters are studied numerically in quenched SU(2) QCD. We determine the effective entropy of the monopole currents which turns out to be a descending function of the blocking scale, indicating that the effective degrees of freedom of the extended monopoles are getting smaller as the blocking scale increases.Comment: 3 pages, 3 figures, uses espcrc2.sty; Lattice2003(topology

Energy- and angle-resolved pump–probe femtosecond photoelectron spectroscopy: Molecular rotation

We have incorporated a classical treatment of molecular rotation into our formulation of energy- and angle-resolved pump–probe photoelectron spectroscopy. This classical treatment provides a useful approach to extracting the photoelectron signal primarily associated with vibrational dynamics in cases where rotational motion is slow and the coupling between rotational and vibrational motion is weak. We illustrate its applicability with pump–probe photoelectron spectra for wave packets on the ^1Σ^+_u double-minimum state of Na_2

Impact of Climate Change on the Santos Harbor, Sao Paulo State (Brazil)

Santos Harbor Area (SHA) in Sao Paulo Coastline (Brazil) is the most important marine cargo transfer terminal in the Southern Hemisphere. A long term relative tidal level variability assessment shows a consistent response to relative sea level rise. A wave data base Wave Watch III was compared with a long term wave data‐base generated by the ERA40‐ECMWF (2003), both local validated. The current bed level of SHA Outer Channel is ‐15.00 m (Chart Datum or, in abbreviation, CD), maintained by dredging. According to the cargo throughput forecast, in 2025, the Access Channel will have to be deepened to level of ‐17.00 m. The feasibility of that choice is discussed from a technical, economical and conceptual navigation point of view in that context. A data set found from a scale model of the whole area of Santos Bay, Estuary and nearby beaches, showed the impact of maritime climate changes upon the coastal area. In the previous researches developed by the authors, it was demonstrated that the wave climate, the tides and tidal currents affect harbor and coastal structures maintenance, beaches stability, tidal inlet, sediment transport, saline intrusion and wetlands. Considering the increasing of the sea hazards and the high values of the infrastructures in that coastline, it is necessary to mitigate the risks. Hence, based on the results obtained by the authors, are highlighted guidelines strategies suggested for Access Channels dimensions, wharves free‐board, jetties dimensions, dredging rates, rigid and flexible littoral defenses and land protection against flooding (including wetlands

Monitoring the effect of a control pulse on a conical intersection by time-resolved photoelectron spectroscopy

We have previously shown how femtosecond angle- and energy-resolved photoelectron spectroscopy can be used to monitor quantum wavepacket bifurcation at an avoided crossing or conical intersection and also how a symmetry-allowed conical intersection can be effectively morphed into an avoided crossing by photo-induced symmetry breaking. The latter result suggests that varying the parameters of a laser to modify a conical intersection might control the rate of passage of wavepackets through such regions, providing a gating process for different chemical products. In this paper, we show with full quantum mechanical calculations that such optical control of conical intersections can actually be monitored in real time with femtosecond angle- and energy-resolved photoelectron spectroscopy. In turn, this suggests that one can optimally control the gating process at a conical intersection by monitoring the photoelectron velocity map images, which should provide far more efficient and rapid optimal control than measuring the ratio of products. To demonstrate the sensitivity of time-resolved photoelectron spectra for detecting the consequences of such optical control, as well as for monitoring how the wavepacket bifurcation is affected by the control, we report results for quantum wavepackets going through the region of the symmetry-allowed conical intersection between the first two ^2A′ states of NO_2 that is transformed to an avoided crossing. Geometry- and energy-dependent photoionization matrix elements are explicitly incorporated in these studies. Time-resolved photoelectron angular distributions and photoelectron images are seen to systematically reflect the effects of the control pulse