Approaches and tools to manipulate the carbonate chemistry

Although the chemistry of ocean acidifi cation is very well understood (see chapter 1), its impact on marine organisms and ecosystems remains poorly known. The biological response to ocean acidifi cation is a recent field of research, the fi rst purposeful experiments have only been carried out as late as the 1980s (Agegian, 1985) and most were not performed until the late 1990s. The potentially dire consequences of ocean acidifi cation have attracted the interest of scientists and students with a limited knowledge of the carbonate chemistry and its experimental manipulation. Perturbation experiments are one of the key approaches used to investigate the biological response to elevated p(CO2). Such experiments are based on measurements of physiological or metabolic processes in organisms and communities exposed to seawater with normal and altered carbonate chemistry. The basics of the carbonate chemistry must be understood to perform meaningful CO2 perturbation experiments (see chapter 1). Briefl y, the marine carbonate system considers € CO2 ∗(aq) [the sum of CO2 and H2CO3], € HCO3 −, € CO3 2−, H+, € OH− , and several weak acid-base systems of which borate-boric acid (€ B(OH)4 − , B(OH)3) is the most important. As discussed by Dickson (chapter 1), if two components of the carbonate chemistry are known, all the other components can be calculated for seawater with typical nutrient concentrations at given temperature, salinity, and pressure. One of the possible pairs is of particular interest because both components can be measured with precision, accuracy, and are conservative in the sense that their concentrations do not change with temperature or pressure. Dissolved inorganic carbon (DIC) is the sum of all dissolved inorganic carbon species while total alkalinity (AT) equals € [HCO3 − ] + 2 € [CO3 2− ] + € [B(OH)4 − ] + € [OH− ] - [H+] + minor components, and refl ects the excess of proton acceptors over proton donors with respect to a zero level of protons (see chapter 1 for a detailed defi nition). AT is determined by the titration of seawater with a strong acid and thus can also be regarded as a measure of the buffering capacity. Any changes in any single component of the carbonate system will lead to changes in several, if not all, other components. In other words, it is not possible to vary a single component of the carbonate system while keeping all other components constant. This interdependency in the carbonate system is important to consider when performing CO2 perturbation experiments. To adjust seawater to different p(CO2) levels, the carbonate system can be manipulated in various ways that usually involve changes in AT or DIC. The goal of this chapter is (1) to examine the benefi ts and drawbacks of various manipulation methods used to date and (2) to provide a simple software package to assist the design of perturbation experiments

Strong field dynamics with ultrashort electron wave packet replicas

We investigate theoretically electron dynamics under a VUV attosecond pulse train which has a controlled phase delay with respect to an additional strong infrared laser field. Using the strong field approximation and the fact that the attosecond pulse is short compared to the excited electron dynamics, we arrive at a minimal analytical model for the kinetic energy distribution of the electron as well as the photon absorption probability as a function of the phase delay between the fields. We analyze the dynamics in terms of electron wave packet replicas created by the attosecond pulses. The absorption probability shows strong modulations as a function of the phase delay for VUV photons of energy comparable to the binding energy of the electron, while for higher photon energies the absorption probability does not depend on the delay, in line with the experimental observations for helium and argon, respectively.Comment: 14 pages, 8 figure

Non-adiabatic molecular association in thermal gases driven by radio-frequency pulses

The molecular association process in a thermal gas of $^{85}$Rb is investigated where the effects of the envelope of the radio-frequency field are taken into account. For experimentally relevant parameters our analysis shows that with increasing pulse length the corresponding molecular conversion efficiency exhibits low-frequency interference fringes which are robust under thermal averaging over a wide range of temperatures. This dynamical interference phenomenon is attributed to St\"uckelberg phase accumulation between the low-energy continuum states and the dressed molecular state which exhibits a shift proportional to the envelope of the radio-frequency pulse intensity.Comment: 5 pages, 3 figure

Effects of precipitation uncertainty on discharge calculations for main river basins

This study quantifies the uncertainty in discharge calculations caused by uncertainty in precipitation input for 294 river basins worldwide. Seven global gridded precipitation datasets are compared at river basin scale in terms of mean annual and seasonal precipitation. The representation of seasonality is similar in all datasets, but the uncertainty in mean annual precipitation is large, especially in mountainous, arctic, and small basins. The average precipitation uncertainty in a basin is 30%, but there are strong differences between basins. The effect of this precipitation uncertainty on mean annual and seasonal discharge was assessed using the uncalibrated dynamic global vegetation and hydrology model Lund-Potsdam-Jena managed land (LPJmL), yielding even larger uncertainties in discharge (average 90%). For 95 basins (out of 213 basins for which measurements were available) calibration of model parameters is problematic because the observed discharge falls within the uncertainty of the simulated discharge. A method is presented to account for precipitation uncertainty in discharge simulations

Quantum dynamics of long-range interacting systems using the positive-P and gauge-P representations

We provide the necessary framework for carrying out stochastic positive-P and gauge-P simulations of bosonic systems with long range interactions. In these approaches, the quantum evolution is sampled by trajectories in phase space, allowing calculation of correlations without truncation of the Hilbert space or other approximations to the quantum state. The main drawback is that the simulation time is limited by noise arising from interactions. We show that the long-range character of these interactions does not further increase the limitations of these methods, in contrast to the situation for alternatives such as the density matrix renormalisation group. Furthermore, stochastic gauge techniques can also successfully extend simulation times in the long-range-interaction case, by making using of parameters that affect the noise properties of trajectories, without affecting physical observables. We derive essential results that significantly aid the use of these methods: estimates of the available simulation time, optimized stochastic gauges, a general form of the characteristic stochastic variance and adaptations for very large systems. Testing the performance of particular drift and diffusion gauges for nonlocal interactions, we find that, for small to medium systems, drift gauges are beneficial, whereas for sufficiently large systems, it is optimal to use only a diffusion gauge. The methods are illustrated with direct numerical simulations of interaction quenches in extended Bose-Hubbard lattice systems and the excitation of Rydberg states in a Bose-Einstein condensate, also without the need for the typical frozen gas approximation. We demonstrate that gauges can indeed lengthen the useful simulation time.Comment: 19 pages, 11 appendix, 3 figure

Femtosecond Photodissociation of Molecules Facilitated by Noise

We investigate the dynamics of diatomic molecules subjected to both a femtosecond mid-infrared laser pulse and Gaussian white noise. The stochastic Schr\"odinger equation with a Morse potential is used to describe the molecular vibrations under noise and the laser pulse. For weak laser intensity, well below the dissociation threshold, it is shown that one can find an optimum amount of noise that leads to a dramatic enhancement of the dissociation probability. The enhancement landscape which is shown as a function of both the noise and the laser strength, exhibits a global maximum. A frequency-resolved gain profile is recorded with a pump-probe set-up which is experimentally realizable. With this profile we identify the linear and nonlinear multiphoton processes created by the interplay between laser and noise and assess their relative contribution to the dissociation enhancement.Comment: 5 pages,5 figure

Optimal Stochastic Enhancement of Photoionization

The effect of noise on the nonlinear photoionization of an atom due to a femtosecond pulse is investigated in the framework of the stochastic Schr\"odinger equation. A modest amount of white noise results in an enhancement of the net ionization yield by several orders of magnitude, giving rise to a form of quantum stochastic resonance. We demonstrate that this effect is preserved if the white noise is replaced by broadband chaotic light.Comment: 4 pages, 4 figure

Attosecond time-scale multi-electron collisions in the Coulomb four-body problem: traces in classical probability densities

In the triple ionization of the Li ground state by single photon absorption the three electrons escape to the continuum mainly through two collision sequences with individual collisions separated by time intervals on the attosecond scale. We investigate the traces of these two collision sequences in the classical probability densities. We show that each collision sequence has characteristic phase space properties which distinguish it from the other. Classical probability densities are the closest analog to quantum mechanical densities allowing our results to be directly compared to quantum mechanical results.Comment: 9 pages, 10 figure