Reactivity of the O2+·(H2O)n and NO+·(H2O)n cluster ions in the D-region of the ionosphere

The protonated water clusters present in the D-region of the ionosphere have been postulated to be formed from cluster ions such as O2+·(H2O)n and NO+·(H2O)n, although the detailed mechanism of the underlying reactions is not understood. Second order Møller–Plesset perturbation theory based Born–Oppenheimer ab initio molecular dynamics (AIMD) simulations of the reactions of the O2+·(H2O)n and NO+·(H2O)n cluster ions to form protonated water clusters reveal different mechanisms for the O2+ and NO+ based ions. AIMD simulations of O2+·(H2O)n=2–5 with initial velocities of the atoms sampled from the Maxwell–Boltzmann distribution at 220 K show that following charge transfer, a reaction to form a protonated water cluster and OH occurs rapidly where the neutral O2 molecule is just a spectator. In contrast, the reaction of NO+·(H2O)n=4,5 has been hypothesised to involve an intracluster reaction, but no reaction is observed in AIMD simulations using thermal initial velocities. However, it is shown that reactions to form protonated water clusters do occur in simulations when a water molecule collides with a NO+·(H2O)4 cluster

Interaction of the NO 3pπ (C 2Π) Rydberg state with RG (RG = Ne, Kr, and Xe): potential energy surfaces and spectroscopy

We present new potential energy surfaces for the interaction of NO(C 2Π) with each of Ne, Kr, and Xe. The potential energy surfaces have been calculated using second order Møller-Plesset perturbation theory, exploiting a procedure to converge the reference Hartree-Fock wavefunction for the excited states: the maximum overlap method. The bound rovibrational states obtained from the surfaces are used to simulate the electronic spectra and their appearance is in good agreement with available (2+1) REMPI spectra. We discuss the assignment and appearance of these spectra, comparing to that of NO-Ar

Trust in climate science and climate scientists: A narrative review

Trust in climate science provides the foundation for evidence-based policymaking on climate change mitigation and adaptation and public perceptions of the urgency of climate change. Here we consider the possibility that lack of public trust in climate science and climate scientists may undermine the effectiveness of climate science communication. To this end, we narratively review three topics of relevance to climate science and climate scientists: 1) The current state of trust; 2) Reasons for distrust; 3) How political engagement affects trust. We then draw on insights from communication and behavioral science to recommend how climate change communicators can become more trustworthy

Coulomb fission in multiply charged molecular clusters: experiment and theory

A series of three multiply charged molecular clusters, (C6H6)nz+ (benzene), (CH3CN)nz+ (acetonitrile), and (C4H8O)nz+ (tetrahydrofuran), where the charge z is either 3 or 4, have been studied for the purpose of identifying patterns of behaviour close to the charge instability limit. Experiments show that on a time scale of ~10-4 s, ions close to the limit undergo Coulomb fission where all of the observed pathways exhibit considerable asymmetry in the sizes of the charged fragments, and are associated with kinetic (ejection) energies of between 1.4 and 2.2 eV. Accurate kinetic energies have been determined through a computer simulation of peak profiles recorded in the experiments and the results modelled using a theory formulated to describe how charged particles of dielectric materials interact with one another (Bichoutskaia et al. J. Chem. Phys. 2010, 133, 024105). The calculated electrostatic interaction energy between separating fragments gives an accurate account for the measured kinetic energies and also supports the conclusion that +4 ions fragment into +3 and +1 products as opposed to the alternative of two +2 fragments. This close match between theory and experiment supports the assumption that a significant fraction of excess charge resides on the surfaces of the fragment ions. It is proposed that the high degree of asymmetry seen in the fragmentation patterns of the multiply charged clusters is due, in part, to limits imposed by the time window during which observations are made

Warfare, Fiscal Capacity, and Performance

We exploit differences in casualties sustained in pre-modern wars to estimate the impact of fiscal capacity on economic performance. In the past, states fought different amounts of external conflicts, of various lengths and magnitudes. To raise the revenues to wage wars, states made fiscal innovations, which persisted and helped to shape current fiscal institutions. Economic historians claim that greater fiscal capacity was the key long-run institutional change brought about by historical conflicts. Using casualties sustained in pre-modern wars to instrument for current fiscal institutions, we estimate substantial impacts of fiscal capacity on GDP per worker. The results are robust to a broad range of specifications, controls, and sub-samples

Does the Supreme Court Follow the Economic Returns? A Response to A Macrotheory of the Court

Today, there is a widespread idea that parents need to learn how to carry out their roles as parents. Practices of parental learning operate throughout society. This article deals with one particular practice of parental learning, namely nanny TV, and the way in which ideal parents are constructed through such programmes. The point of departure is SOS family, a series broadcast on Swedish television in 2008. Proceeding from the theorising of governmentality developed in the wake of the work of Michel Foucault, we analyse the parental ideals conveyed in the series, as an example of the way parents are constituted as subjects in the ‘advanced liberal society’ of today. The ideal parent is a subject who, guided by the coach, is constantly endeavouring to achieve a makeover. The objective of this endeavour, however, is self-control, whereby the parents will in the end become their own coaches.

Newborn screening for medium chain acyl-CoA dehydrogenase deficiency in England: prevalence, predictive value and test validity based on 1.5 million screened babies

Medium chain acyl-CoA dehydrogenase deficiency (MCADD) is a rare, life-threatening condition. Early diagnosis by screening asymptomatic newborns may improve outcome, but the benefit to newborns identified with variants not encountered clinically is uncertain

Quantum chemical calculations of X-ray emission spectroscopy

The calculation of X-ray emission spectroscopy with equation of motion coupled cluster theory (EOM-CCSD), time dependent density functional theory (TDDFT) and resolution of the identity single excitation configuration interaction with second order perturbation theory (RI-CIS(D)) is studied. These methods can be applied to calculate X-ray emission transitions by using a reference determinant with a core-hole, and they provide a convenient approach to compute the X-ray emission spectroscopy of large systems since all of the required states can be obtained within a single calculation removing the need to perform a separate calculation for each state. For all of the methods, basis sets with the inclusion of additional basis functions to describe core orbitals are necessary, particularly when studying transitions involving the 1s or- bitals of heavier nuclei. EOM-CCSD predicts accurate transition energies when compared with experiment, however, its application to larger systems is restricted by its computational cost and difficulty in converging the CCSD equations for a core-hole reference determinant, which become increasing problematic as the size of the system studied increases. While RI-CIS(D) gives accurate transition energies for small molecules containing first row nuclei, its application to larger systems is limited by the CIS states providing a poor zeroth order reference for perturbation theory which leads to very large errors in the computed transition energies for some states. TDDFT with standard exchange-correlation functionals predicts transition energies that are much larger than experiment. Optimization of a hybrid and short-range cor- rected functional to predict the X-ray emission transitions results in much closer agreement with EOM-CCSD. The most accurate exchange-correlation functional identified is a modified B3LYP hybrid functional with 66% Hartree-Fock exchange, denoted B66LYP, which predicts X-ray emission spectra for a range of molecules including fluorobenzene, nitrobenzene, ace- tone, dimethyl sulfoxide and CF3Cl in good agreement with experiment

Soliton Interactions in Perturbed Nonlinear Schroedinger Equations

We use multiscale perturbation theory in conjunction with the inverse scattering transform to study the interaction of a number of solitons of the cubic nonlinear Schroedinger equation under the influence of a small correction to the nonlinear potential. We assume that the solitons are all moving with the same velocity at the initial instant; this maximizes the effect each soliton has on the others as a consequence of the perturbation. Over the long time scales that we consider, the amplitudes of the solitons remain fixed, while their center of mass coordinates obey Newton's equations with a force law for which we present an integral formula. For the interaction of two solitons with a quintic perturbation term we present more details since symmetries -- one related to the form of the perturbation and one related to the small number of particles involved -- allow the problem to be reduced to a one-dimensional one with a single parameter, an effective mass. The main results include calculations of the binding energy and oscillation frequency of nearby solitons in the stable case when the perturbation is an attractive correction to the potential and of the asymptotic "ejection" velocity in the unstable case. Numerical experiments illustrate the accuracy of the perturbative calculations and indicate their range of validity.Comment: 28 pages, 7 figures, Submitted to Phys Rev E Revised: 21 pages, 6 figures, To appear in Phys Rev E (many displayed equations moved inline to shorten manuscript