Mode-specific reactivity of CH4 on Pt(110)-(1Ã2): The concerted role of stretch and bend excitation

The state-resolved reaction probability of CH4 on Pt�110-�1�2 was measured as a function of CH4 translational energy for four vibrational eigenstates comprising different amounts of C-H stretch and bend excitation. Mode-specific reactivity is observed both between states from different polyads and between isoenergetic states belonging to the same polyad of CH4. For the stretch/bend combination states, the vibrational efficacy of reaction activation is observed to be higher than for either pure C-H stretching or pure bending states, demonstrating a concerted role of stretch and bend excitation in C-H bond scission. This concerted role, reflected by the nonadditivity of the vibrational efficacies, is consistent with transition state structures found by ab initio calculations and indicates that current dynamical models of CH4 chemisorption neglect an important degree of freedom by including only C-H stretching motion.

North Atlantic subtropical mode waters and ocean memory in HadCM3

A study of the formation and propagation of volume anomalies in North Atlantic Mode Waters is presented, based on 100 yr of monthly mean fields taken from the control run of the Third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3). Analysis of the temporal and. spatial variability in the thickness between pairs of isothermal surfaces bounding the central temperature of the three main North Atlantic subtropical mode waters shows that large-scale variability in formation occurs over time scales ranging from 5 to 20 yr. The largest formation anomalies are associated with a southward shift in the mixed layer isothermal distribution, possibly due to changes in the gyre dynamics and/or changes in the overlying wind field and air-sea heat fluxes. The persistence of these anomalies is shown to result from their subduction beneath the winter mixed layer base where they recirculate around the subtropical gyre in the background geostrophic flow. Anomalies in the warmest mode (18 degrees C) formed on the western side of the basin persist for up to 5 yr. They are removed by mixing transformation to warmer classes and are returned to the seasonal mixed layer near the Gulf Stream where the stored heat may be released to the atmosphere. Anomalies in the cooler modes (16 degrees and 14 degrees C) formed on the eastern side of the basin persist for up to 10 yr. There is no clear evidence of significant transformation of these cooler mode anomalies to adjacent classes. It has been proposed that the eastern anomalies are removed through a tropical-subtropical water mass exchange mechanism beneath the trade wind belt (south of 20 degrees N). The analysis shows that anomalous mode water formation plays a key role in the long-term storage of heat in the model, and that the release of heat associated with these anomalies suggests a predictable climate feedback mechanism.

A singular vector perspective of 4DVAR: The spatial structure and evolution of baroclinic weather systems

The extent to which the four-dimensional variational data assimilation (4DVAR) is able to use information about the time evolution of the atmosphere to infer the vertical spatial structure of baroclinic weather systems is investigated. The singular value decomposition (SVD) of the 4DVAR observability matrix is introduced as a novel technique to examine the spatial structure of analysis increments. Specific results are illustrated using 4DVAR analyses and SVD within an idealized 2D Eady model setting. Three different aspects are investigated. The first aspect considers correcting errors that result in normal-mode growth or decay. The results show that 4DVAR performs well at correcting growing errors but not decaying errors. Although it is possible for 4DVAR to correct decaying errors, the assimilation of observations can be detrimental to a forecast because 4DVAR is likely to add growing errors instead of correcting decaying errors. The second aspect shows that the singular values of the observability matrix are a useful tool to identify the optimal spatial and temporal locations for the observations. The results show that the ability to extract the time-evolution information can be maximized by placing the observations far apart in time. The third aspect considers correcting errors that result in nonmodal rapid growth. 4DVAR is able to use the model dynamics to infer some of the vertical structure. However, the specification of the case-dependent background error variances plays a crucial role.

Stratosphere‐troposphere coupling and annular mode variability in chemistry‐climate models

The internal variability and coupling between the stratosphere and troposphere in CCMVal‐2 chemistry‐climate models are evaluated through analysis of the annular mode patterns of variability. Computation of the annular modes in long data sets with secular trends requires refinement of the standard definition of the annular mode, and a more robust procedure that allows for slowly varying trends is established and verified. The spatial and temporal structure of the models’ annular modes is then compared with that of reanalyses. As a whole, the models capture the key features of observed intraseasonal variability, including the sharp vertical gradients in structure between stratosphere and troposphere, the asymmetries in the seasonal cycle between the Northern and Southern hemispheres, and the coupling between the polar stratospheric vortices and tropospheric midlatitude jets. It is also found that the annular mode variability changes little in time throughout simulations of the 21st century. There are, however, both common biases and significant differences in performance in the models. In the troposphere, the annular mode in models is generally too persistent, particularly in the Southern Hemisphere summer, a bias similar to that found in CMIP3 coupled climate models. In the stratosphere, the periods of peak variance and coupling with the troposphere are delayed by about a month in both hemispheres. The relationship between increased variability of the stratosphere and increased persistence in the troposphere suggests that some tropospheric biases may be related to stratospheric biases and that a well‐simulated stratosphere can improve simulation of tropospheric intraseasonal variability.

The excitation of ionospheric convection

This review presents recent observations of high-latitude ionospheric plasma convection, obtained using the EISCAT radar in the 'Polar' experiment mode. The paper is divided into two main parts. Firstly, the delay in the response of dayside high-latitude flows to changes in the interplanetary magnetic field is discussed. The results show the importance for the excitation of dayside convection of the transfer of magnetic flux from the dayside into the tail lobe. Consequently, ionospheric convection should be thought of as the sum of two intrinsically time-dependent flow patterns. The first of these patterns is directly driven by solar wind-magnetosphere coupling, dominates ionospheric flows on the dayside, is associated with an expanding polar cap area and is the F-region flow equivalent of the DP-2 E-region current system. The second of the two patterns is driven by the release of energy stored in the geomagnetic tail, dominates ionospheric flows on the nightside, is associated with a contracting polar cap and is equivalent to the DP-1, or substorm, current system. In the second half of the paper, various transient flow bursts observed in the vicinity of the dayside cusp are studied. These radar data, combined with simultaneous optical observations of transient dayside aurorae, strongly suggest that momentum is transferred across the magnetopause and into the ionosphere in a series of bursts, each associated with voltages of 30-80 kV. Similarities between these bursts and flux transfer events observed at the magnetopause are discussed.

Mode-specific chemisorption of CH4 on Pt{110}-(1 x 2) explored by first-principles molecular dynamics

The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability