Infrared action spectroscopy of nitrous oxide on cationic gold and cobalt clusters

Understanding the catalytic decomposition of nitrous oxide on finely divided transition metals is an important environmental issue. In this study, we present the results of a combined infrared action spectroscopy and quantum chemical investigation of molecular N2O binding to isolated Aun+ (n ≤ 7) and Con+ (n ≤ 5) clusters. Infrared multiple-photon dissociation spectra have been recorded in the regions of both the N=O (1000–1400 cm-1) and N=N (2100–2450 cm-1) stretching modes of nitrous oxide. In the case of Aun+ clusters only the ground electronic state plays a role, while the involvement of energetically low-lying excited states in binding to the Con+ clusters cannot be ruled out. There is a clear preference for N-binding to clusters of both metals but some O-bound isomers are observed in the case of smaller Con(N2O)+ clusters

Observation of electron transfer mediated decay in aqueous solution

Photoionization is at the heart of X ray photoelectron spectroscopy XPS , which gives access to important information on a sample s local chemical environment. Local and non local electronic decay after photoionization in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively have been well studied. However, electron transfer mediated decay ETMD , which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low energy electrons using liquid microjet soft XPS. Experimental results are interpreted using molecular dynamics and high level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion solvent distances and solvent arrangemen

Stochastic reliable control of a class of uncertain time-delay systems with unknown nonlinearities

Copyright [2001] IEEE. This material is posted here with permission of the IEEE. Such permission of the IEEE does not in any way imply IEEE endorsement of any of Brunel University's products or services. Internal or personal use of this material is permitted. However, permission to reprint/republish this material for advertising or promotional purposes or for creating new collective works for resale or redistribution must be obtained from the IEEE by writing to [email protected]. By choosing to view this document, you agree to all provisions of the copyright laws protecting it.This paper investigates the robust reliable control problem for a class of nonlinear time-delay stochastic systems. The system under study involves stochastics, state time-delay, parameter uncertainties, possible actuator failures and unknown nonlinear disturbances, which are often encountered in practice and the sources of instability. Our attention is focused on the design of linear state feedback memoryless controllers such that, for all admissible uncertainties as well as actuator failures occurring among a prespecified subset of actuators, the plant remains stochastically exponentially stable in mean square, independent of the time delay. Sufficient conditions are proposed to guarantee the desired robust reliable exponential stability despite possible actuator failures, which are in terms of the solutions to algebraic Riccati inequalities. An illustrative example is exploited to demonstrate the applicability of the proposed design approac