Simulating conical intersection dynamics in the condensed phase with hybrid quantum master equations

We present a framework for simulating relaxation dynamics through a conical intersection of an open quantum system that combines methods to approximate the motion of degrees of freedom with disparate time and energy scales. In the vicinity of a conical intersection, a few degrees of freedom render the nuclear dynamics nonadiabatic with respect to the electronic degrees of freedom. We treat these strongly coupled modes by evolving their wavepacket dynamics in the absence of additional coupling exactly. The remaining weakly coupled nuclear degrees of freedom are partitioned into modes that are fast relative to the nonadiabatic coupling and those that are slow. The fast degrees of freedom can be traced out and treated with second-order perturbation theory in the form of the time-convolutionless master equation. The slow degrees of freedom are assumed to be frozen over the ultrafast relaxation, and treated as sources of static disorder. In this way, we adopt the recently developed frozen-mode extension to second-order quantum master equations. We benchmark this approach to numerically exact results in models of pyrazine internal conversion and rhodopsin photoisomerization. We use this framework to study the dependence of the quantum yield on the reorganization energy and the characteristic timescale of the bath, in a two-mode model of photoisomerization. We find that the yield is monotonically increasing with reorganization energy for a Markovian bath, but monotonically decreasing with reorganization energy for a non-Markovian bath. This reflects the subtle interplay between dissipation and decoherence in conical intersection dynamics in the condensed phase

Ray methods for Free Boundary Problems

We discuss the use of the WKB ansatz in a variety of parabolic problems involving a small parameter. We analyse the Stefan problem for small latent heat, the Black--Scholes problem for an American put option, and some nonlinear diffusion equations, in each case constructing an asymptotic solution by the use of ray methods

Atypical Work and Employment Continuity

Atypical employment arrangements such as agency temporary work and contracting have long been criticized as offering more precarious and unstable work than regular employment. Using data from two datasets – the CAEAS and the NLSY79 – we determine whether workers who take such jobs rather than regular employment, or the alternative of continued job search, subsequently experience greater or lesser employment continuity. Observed differences between the various working arrangements are starkest when we do not account for unobserved individual heterogeneity. Controlling for the latter, we report that the advantage of regular work over atypical work and atypical work over continued joblessness dissipates.employment continuity, open-ended work, atypical work, unemployment, inactivity

‘Atypical Work’ and Compensation

Atypical work, or alternative work arrangements in U.S. parlance, has long been criticized in popular debate as providing poorly-compensated employment. Although the early U.S. literature seemed to confirm this perception, more recent cet. par. analysis has offered a partial but somewhat more optimistic evaluation. The present paper builds on the latter body of research with a view to providing improved estimates of the effect of the full range alternative work arrangements on worker compensation. The improvements are basically two-fold. First, we account for the skewness in atypical worker earnings while retaining the Mincerian human capital earnings function. Second, we deploy additional waves of the main dataset on atypical workers (the CAEAS), while supplementing this cross-section analysis with longitudinal data from the NLSY. Our analysis covers earnings and (access to) health benefits. We report that although one group of atypical workers (contractors) seems to enjoy a wage premium, cross-section results from the CPS and NLSY for the better-known category of temporary workers point to a negative wage differential of some 6-15 percent. It emerges that much of the disparity stems from unobserved worker heterogeneity, accounting for which still supports a wage advantage for contracting work. As far as fringes are concerned, the appearance in cross section of a potentially large deficit in access to health benefits is again reduced after accounting for the permanent unobserved individual heterogeneity, although in this case the attenuation is much more modest.atypical/contingent work, alternative work arrangements, wage differentials, employer-related health insurance

The demise of a model? The state of collective bargaining and worker representation in Germany.

This article investigates collective bargaining trends in the German private sector since 2000. Using data from the IAB Establishment Panel and the German Establishment History Panel, it provides both cross-sectional and longitudinal evidence on these developments. It confirms that the hemorrhaging of sectoral bargaining, first observed in the 1980s and 1990s, is ongoing. Furthermore, works councils are also in decline, so that the dual system also displays erosion. For their part, any increases in collective bargaining at firm level have been minimal in recent years, while the behavior of newly-founded and closing establishments does not seem to lie at the root of a burgeoning collective bargaining free sector. Although there are few obvious signs of an organic reversal of the process, some revitalization of the bargaining system from above is implied by the labor policies of the new coalition government

Studying rare nonadiabatic dynamics with transition path sampling quantum jump trajectories

We present a method to study rare nonadiabatic dynamics in open quantum systems using transition path sampling and quantum jump trajectories. As with applications of transition path sampling to classical dynamics, the method does not rely on prior knowledge of transition states or reactive pathways, and thus can provide mechanistic insight into ultrafast relaxation processes in addition to their associated rates. In particular, we formulate a quantum path ensemble using the stochastic realizations of an unravelled quantum master equation, which results in trajectories that can be conditioned on starting and ending in particular quantum states. Because the dynamics rigorously obeys detailed balance, rate constants can be evaluated from reversible work calculations in this conditioned ensemble, allowing for branching ratios and yields to be computed in an unbiased manner. We illustrate the utility of this method with three examples: energy transfer in a donor-bridge-acceptor model, and models of photo-induced proton-coupled electron transfer and thermally activated electron transfer. These examples demonstrate the efficacy of path ensemble methods and pave the way for their use in studying of complex reactive quantum dynamics

A Spin-Orbit Alignment for the Hot Jupiter HATS-3b

We have measured the alignment between the orbit of HATS-3b (a recently discovered, slightly inflated Hot Jupiter) and the spin-axis of its host star. Data were obtained using the CYCLOPS2 optical-fiber bundle and its simultaneous calibration system feeding the UCLES spectrograph on the Anglo-Australian Telescope. The sky-projected spin-orbit angle of $\lambda = 3\pm25^{\circ}$ was determined from spectroscopic measurements of Rossiter-McLaughlin effect. This is the first exoplanet discovered through the HATSouth transit survey to have its spin-orbit angle measured. Our results indicate that the orbital plane of HATS-3b is consistent with being aligned to the spin axis of its host star. The low obliquity of the HATS-3 system, which has a relatively hot mid F-type host star, agrees with the general trend observed for Hot Jupiter host stars with effective temperatures $>6250$K to have randomly distributed spin-orbit angles.Comment: 13 pages. Accepted for publication in the Astrophysical Journa