Ultrafast Relaxation Dynamics of Osmium-Polypyridine Complexes in Solution

We present steady-state absorption and emission spectroscopy and femtosecond broadband photoluminescence up-conversion spectroscopy studies of the electronic relaxation of Os(dmbp)3 (Os1) and Os(bpy)2(dpp) (Os2) in ethanol, where dmbp is 4,4′-dimethyl-2,2′-biypridine, bpy is 2,2′-biypridine, and dpp is 2,3-dipyridyl pyrazine. In both cases, the steady-state phosphorescence is due to the lowest 3MLCT state, whose quantum yield we estimate to be ≤5.0 × 10–3. For Os1, the steady-state phosphorescence lifetime is 25 ns. In both complexes, the photoluminescence excitation spectra map the absorption spectrum, pointing to an excitation wavelength-independent quantum yield. The ultrafast studies revealed a short-lived (≤100 fs) fluorescence, which stems from the lowest singlet metal-to-ligand-charge-transfer (1MLCT) state and decays by intersystem crossing to the manifold of 3MLCT states. In addition, Os1 exhibits a 50 ps lived emission from an intermediate triplet state at an energy 2000 cm–1 above that of the long-lived (25 ns) phosphorescence. In Os2, the 1MLCT–3MLCT intersystem crossing is faster than that in Os1, and no emission from triplet states is observed other than the lowest one. These observations are attributed to a higher density of states or a smaller energy spacing between them compared with Os1. They highlight the importance of the energetics on the rate of intersystem crossing.

Dynamics of the last four glacial terminations recorded in Lake Van, Turkey

A well-dated suite of Lake Van climate-proxy data covering the last 360 ka documents environmental changes over 4 glacial/interglacial cycles in Eastern Anatolia, Turkey. The picture of cold and dry glacials and warm and wet interglacials emerging from pollen, organic carbon, authigenic carbonate content, elemental profiling by XRF and lithological analyses is inconsistent with classical interpretation of ox- ygen isotopic composition of carbonates pointing to a more complex pattern in Lake Van region. Detailed analysis of glacial terminations allows for the constraining of a depositional model explaining different patterns observed in all the proxies. We hypothesize that variations in relative contribution of rainfall, snowmelt and glacier meltwater recharging the basin have a very important role for all sedimentary processes in Lake Van. Lake level of glacial Lake Van, predominantly fed by snowmelt, was low, the water column was oxic, and carbonates precipitating in the epilimnion recorded the light isotopic signature of inflow. During terminations, increasing rainfall and significant supply of mountain glaciers' meltwater contributed to lake level rise. Increased rainfall enhanced density gradients in the water column, and hindered mixing leading to development of bottom-water anoxia. Carbonates precipitating during terminations show large fluctuations in their isotopic composition. Full interglacial conditions in Lake Van are characterized by high or slowly falling lake level. Rainfall and snowmelt feed the lake but due to re-established mixing, the isotopic composition of authigenic carbonates is heavier and closer to that of evaporation-influenced lake water than that of runoff representing snowmelt and atmospheric precipitation.

ANALYTICAL MODELS OF EXOPLANETARY ATMOSPHERES. I. ATMOSPHERIC DYNAMICS VIA THE SHALLOW WATER SYSTEM

Within the context of exoplanetary atmospheres, we present a comprehensive linear analysis of forced, damped, magnetized shallow water systems, exploring the effects of dimensionality, geometry (Cartesian, pseudo-spherical, and spherical), rotation, magnetic tension, and hydrodynamic and magnetic sources of friction. Across a broad range of conditions, we find that the key governing equation for atmospheres and quantum harmonic oscillators are identical, even when forcing (stellar irradiation), sources of friction (molecular viscosity, Rayleigh drag, and magnetic drag), and magnetic tension are included. The global atmospheric structure is largely controlled by a single key parameter that involves the Rossby and Prandtl numbers. This near-universality breaks down when either molecular viscosity or magnetic drag acts non-uniformly across latitude or a poloidal magnetic field is present, suggesting that these effects will introduce qualitative changes to the familiar chevron-shaped feature witnessed in simulations of atmospheric circulation. We also find that hydrodynamic and magnetic sources of friction have dissimilar phase signatures and affect the flow in fundamentally different ways, implying that using Rayleigh drag to mimic magnetic drag is inaccurate. We exhaustively lay down the theoretical formalism (dispersion relations, governing equations, and time-dependent wave solutions) for a broad suite of models. In all situations, we derive the steady state of an atmosphere, which is relevant to interpreting infrared phase and eclipse maps of exoplanetary atmospheres. We elucidate a pinching effect that confines the atmospheric structure to be near the equator. Our suite of analytical models may be used to develop decisively physical intuition and as a reference point for three-dimensional magnetohydrodynamic simulations of atmospheric circulation.

Two-dimensional Lattice Gauge Theories with Superconducting Quantum Circuits

A quantum simulator of U(1) lattice gauge theories can be implemented with superconducting circuits. This allows the investigation of confined and deconfined phases in quantum link models, and of valence bond solid and spin liquid phases in quantum dimer models. Fractionalized confining strings and the real-time dynamics of quantum phase transitions are accessible as well. Here we show how state-of-the-art superconducting technology allows us to simulate these phenomena in relatively small circuit lattices. By exploiting the strong non-linear couplings between quantized excitations emerging when superconducting qubits are coupled, we show how to engineer gauge invariant Hamiltonians, including ring-exchange and four-body Ising interactions. We demonstrate that, despite decoherence and disorder effects, minimal circuit instances allow us to investigate properties such as the dynamics of electric flux strings, signaling confinement in gauge invariant field theories. The experimental realization of these models in larger superconducting circuits could address open questions beyond current computational capability.

Crystalline Confinement

We show that exotic phases arise in generalized lattice gauge theories known as quantum link models in which classical gauge fields are replaced by quantum operators. While these quantum models with discrete variables have a finite-dimensional Hilbert space per link, the continuous gauge symmetry is still exact. An efficient cluster algorithm is used to study these exotic phases. The (2+1)-d system is confining at zero temperature with a spontaneously broken translation symmetry. A crystalline phase exhibits confinement via multi stranded strings between chargeanti-charge pairs. A phase transition between two distinct confined phases is weakly first order and has an emergent spontaneously broken approximate SO(2) global symmetry. The low-energy physics is described by a (2 + 1)-d RP(1) effective field theory, perturbed by a dangerously irrelevant SO(2) breaking operator, which prevents the interpretation of the emergent pseudo-Goldstone boson as a dual photon. This model is an ideal candidate to be implemented in quantum simulators to study phenomena that are not accessible using Monte Carlo simulations such as the real-time evolution of the confining string and the real-time dynamics of the pseudo-Goldstone boson.

Real-time simulation of large open quantum spin systems driven by dissipation

We consider a large quantum system with spins 12 whose dynamics is driven entirely by measurements of the total spin of spin pairs. This gives rise to a dissipative coupling to the environment. When one averages over the measurement results, the corresponding real-time path integral does not suffer from a sign problem. Using an efficient cluster algorithm, we study the real-time evolution from an initial antiferromagnetic state of the two-dimensional Heisenberg model, which is driven to a disordered phase, not by a Hamiltonian, but by sporadic measurements or by continuous Lindblad evolution.

Towards quantum simulating QCD

Quantum link models provide an alternative non-perturbative formulation of Abelian and non-Abelian lattice gauge theories. They are ideally suited for quantum simulation, for example, using ultracold atoms in an optical lattice. This holds the promise to address currently unsolvable problems, such as the real-time and high-density dynamics of strongly interacting matter, first in toy-model gauge theories, and ultimately in QCD.

Energy and charge transfer dynamics in DNA based light harvesting antennae

DNA can serve as a versatile scaffold for chromophore assemblies. For example, light-harvesting antennae have been realized by incorporating phenanthrene and pyrene building blocks into DNA strands. It was shown that by exciting at 320 nm (absorption of phenanthrene), an emission at 450 nm is observed which corresponds to a phenanthrene-pyrene exciplex. The more phenanthrenes are added into the DNA duplex, the higher is the fluorescence intensity with no significant change in quantum yield. This shows that phenanthrene acts as a donor and efficiently transfers the excitation energy to the pyrene. Up to now, the mechanism of this energy transfer and exciplex formation is not known. Therefore, we first aim at studying the photo-cycle of such DNA assemblies through transient absorption spectroscopy. Based on the results, we will explore ways to manipulate the energy transfer by application of intense THz fields. Ground as well as excited state Stark effect dynamics will be investigated.

Real-time simulation of nonequilibrium transport of magnetization in large open quantum spin systems driven by dissipation

Using quantum Monte Carlo, we study the nonequilibrium transport of magnetization in large open strongly correlated quantum spin-12 systems driven by purely dissipative processes that conserve the uniform or staggered magnetization, disregarding unitary Hamiltonian dynamics. We prepare both a low-temperature Heisenberg ferromagnet and an antiferromagnet in two parts of the system that are initially isolated from each other. We then bring the two subsystems in contact and study their real-time dissipative dynamics for different geometries. The flow of the uniform or staggered magnetization from one part of the system to the other is described by a diffusion equation that can be derived analytically.

Quantum Nondemolition Measurement Enables Macroscopic Leggett-Garg Tests

We show how a test of macroscopic realism based on Leggett-Garg inequalities (LGIs) can be performed in a macroscopic system. Using a continuous-variable approach, we consider quantum nondemolition (QND) measurements applied to atomic ensembles undergoing magnetically driven coherent oscillation. We identify measurement schemes requiring only Gaussian states as inputs and giving a significant LGI violation with realistic experimental parameters and imperfections. The predicted violation is shown to be due to true quantum effects rather than to a classical invasivity of the measurement. Using QND measurements to tighten the “clumsiness loophole” forces the stubborn macrorealist to recreate quantum backaction in his or her account of measurement.

Dynamics of dissipative Bose-Einstein condensation

We resolve the real-time dynamics of a purely dissipative s=1/2 quantum spin or, equivalently, hard-core boson model on a hypercubic d-dimensional lattice. The considered quantum dissipative process drives the system to a totally symmetric macroscopic superposition in each of the S3 sectors. Different characteristic time scales are identified for the dynamics and we determine their finite-size scaling. We introduce the concept of cumulative entanglement distribution to quantify multiparticle entanglement and show that the considered protocol serves as an efficient method to prepare a macroscopically entangled Bose-Einstein condensate.

Dynamics of the Developing Chick Chorioallantoic Membrane Assessed by Stereology, Allometry, Immunohistochemistry and Molecular Analysis.

The chick chorioallantoic membrane (CAM) is a widely used model for the study of angiogenesis, tumour growth, as well as drug efficacy. In spite of this, little is known about the developmental alteration from its appearance to the time of hatching. In the current study the CAM has been studied by classical stereology and allometry. Expression levels of selected angiogenesis-related molecules were estimated by RT-PCR and cell dynamics assessed by proliferation and apoptosis assays. Absolute CAM volume increased from a low of 0.47 ± 0.11 cm3 at embryonic day 8 (E8) to a high of 2.05 ± 0.27 cm3 at E18, and then decreased to 1.6 ± 0.47 cm3 at E20. On allometric analysis, three growth phases were identifiable. Between E8-13 (phase I), the CAM grew fastest; moderately in phase II (E13-18) but was regressing in phase III (E18-20). The chorion, the mesenchyme and the allantoic layers grew fastest in phase I, but moderately in phase II. The mesenchyme grew slowly in phase III while the chorion and allantois were regressing. Chorionic cell volume increased fastest in phase I and was regressing in phase III. Chorionic capillaries grew steadily in phase I and II but regressed in phase III. Both the chorion and the allantois grew by intrinsic cell proliferation as well as recruitment of cells from the mesenchyme. Cell proliferation was prominent in the allantois and chorion early during development, declined after E17 and apoptosis started mainly in the chorion from E14. VEGFR2 expression peaked at E11 and declined steadily towards E20, VEGF peaked at E13 and E20 while HIF 1α had a peak at E11 and E20. Studies targeting CAM growth and angiogenesis need to take these growth phases into consideration.