Work fluctuation theorems for harmonic oscillators

The work fluctuations of an oscillator in contact with a thermostat and driven out of equilibrium by an external force are studied experimentally and theoretically within the context of Fluctuation Theorems (FTs). The oscillator dynamics is modeled by a second order Langevin equation. Both the transient and stationary state fluctuation theorems hold and the finite time corrections are very different from those of a first order Langevin equation. The periodic forcing of the oscillator is also studied; it presents new and unexpected short time convergences. Analytical expressions are given in all cases

Western Mediterranean precipitation over the last 300 years from instrumental observations

The paper reports the results of the analysis of the 14 longest precipitation instrumental series, covering the last 300 years, that have been recovered in six subareas of the Western Mediterranean basin, i.e., Portugal, Northern and Southern Spain, Southern France, Northern and Southern Italy. This study extends back by one century our knowledge about the instrumental precipitation over theWestern Mediterranean, and by two centuries in some specific subareas. All the time series show repeated swings. No specific trends have been found over the whole period, except in a few cases, but with modest time changes and sometimes having opposite tendency. The same can be said for the most recent decades although with some more marked departures from the average. The correlation between the various Mediterranean subareas is generally not significant, or almost uncorrelated. The Wavelet Spectral Analysis applied to the precipitation identifies only a minor 56-year cycle in autumn, i.e., the same return period that has been found in literature for the Sea Surface Temperature over North Atlantic. A comparison with a gridded dataset reconstruction based on mixed multiproxy and instrumental observations, shows that the grid reconstruction is in good agreement with the observed data for the period after 1900, less for the previous period

Learning, Social Intelligence and the Turing Test - why an "out-of-the-box" Turing Machine will not pass the Turing Test

The Turing Test (TT) checks for human intelligence, rather than any putative general intelligence. It involves repeated interaction requiring learning in the form of adaption to the human conversation partner. It is a macro-level post-hoc test in contrast to the definition of a Turing Machine (TM), which is a prior micro-level definition. This raises the question of whether learning is just another computational process, i.e. can be implemented as a TM. Here we argue that learning or adaption is fundamentally different from computation, though it does involve processes that can be seen as computations. To illustrate this difference we compare (a) designing a TM and (b) learning a TM, defining them for the purpose of the argument. We show that there is a well-defined sequence of problems which are not effectively designable but are learnable, in the form of the bounded halting problem. Some characteristics of human intelligence are reviewed including it's: interactive nature, learning abilities, imitative tendencies, linguistic ability and context-dependency. A story that explains some of these is the Social Intelligence Hypothesis. If this is broadly correct, this points to the necessity of a considerable period of acculturation (social learning in context) if an artificial intelligence is to pass the TT. Whilst it is always possible to 'compile' the results of learning into a TM, this would not be a designed TM and would not be able to continually adapt (pass future TTs). We conclude three things, namely that: a purely "designed" TM will never pass the TT; that there is no such thing as a general intelligence since it necessary involves learning; and that learning/adaption and computation should be clearly distinguished.Comment: 10 pages, invited talk at Turing Centenary Conference CiE 2012, special session on "The Turing Test and Thinking Machines

Dilute ferrimagnetic semiconductors in Fe-substituted spinel ZnGa2_2O4_4

Solid solutions of nominal composition [ZnGa$_2$O$_4$]$_{1-x}$[Fe$_3$O$_4$]$_x$, of the semiconducting spinel ZnGa$_2$O$_4$ with the ferrimagnetic spinel Fe$_3$O$_4$ have been prepared with $x$ = 0.05, 0.10, and 0.15. All samples show evidence for long-range magnetic ordering with ferromagnetic hysteresis at low temperatures. Magnetization as a function of field for the $x$ = 0.15 sample is S-shaped at temperatures as high as 200 K. M\"ossbauer spectroscopy on the $x$ = 0.15 sample confirms the presence of Fe$^{3+}$, and spontaneous magnetization at 4.2 K. The magnetic behavior is obtained without greatly affecting the semiconducting properties of the host; diffuse reflectance optical spectroscopy indicates that Fe substitution up to $x$ = 0.15 does not affect the position of the band edge absorption. These promising results motivate the possibility of dilute ferrimagnetic semiconductors which do not require carrier mediation of the magnetic moment.Comment: 9 pages and 6 figure

Intramolecular vibronic dynamics in molecular solids: C60

Vibronic coupling in solid C60 has been investigated with a combination of resonant photoemission spectroscopy (RPES) and resonant inelastic x-ray scattering (RIXS). Excitation as a function of energy within the lowest unoccupied molecular orbital resonance yielded strong oscillations in intensity and dispersion in RPES, and a strong inelastic component in RIXS. Reconciling these two observations establishes that vibronic coupling in this core hole excitation leads to predominantly inelastic scattering and localization of the excited vibrations on the molecule on a femtosecond time scale. The coupling extends throughout the widths of the frontier valence bands.

Ce-L3-XAS study of the temperature dependence of the 4f occupancy in the Kondo system Ce2Rh3Al9

We have used temperature dependent x-ray absorption at the Ce-L3 edge to investigate the recently discovered Kondo compound Ce2Rh3Al9. The systematic changes of the spectral lineshape with decreasing temperature are analyzed and found to be related to a change in the $4f$ occupation number, n_f, as the system undergoes a transition into a Kondo state. The temperature dependence of $n_f$ indicates a characteristic temperature of 150K, which is clearly related with the high temperature anomaly observed in the magnetic susceptibility of the same system. The further anomaly observed in the resistivity of this system at low temperature (ca. 20K) has no effect on n_f and is thus not of Kondo origin.Comment: 7 pages, three figures, submitted to PR

Overturning established chemoselectivities : selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors

The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates