Vibrational spectra of α-amino acids in the zwitterionic state in aqueous solution and the solid state: DFT calculations and the influence of hydrogen bonding

The zwitterionic forms of the two simplest alpha-amino acids, glycine and l-alanine, in aqueous solution and the solid state have been modeled by DFT calculations. Calculations of the structures in the solid state, using PW91 or PBE functionals, are in good agreement with the reported crystal structures, and the vibrational spectra computed at the optimized geometries provide a good fit to the observed IR and Raman spectra in the solid state. DFT calculations of the structures and vibrational spectra of the zwitterions in aqueous solution at the B3-LYP/cc-pVDZ level were found to require both explicit and implicit solvation models. Explicit solvation was modeled by inclusion of five hydrogen-bonded water molecules attached to each of the five possible hydrogen-bonding sites in the zwitterion and the integration equation formalism polarizable continuum model (IEF-PCM) was employed, providing a satisfactory fit to observed IR and Raman spectra. Band assignments are reported in terms of potential-energy distributions, which differ in some respects to those previously reported for glycine and l-alanine.

Birth-death processes with mass annihilation and state-dependent immigration

A birth-death process is subject to mass annihilation at rate β with subsequent mass immigration occurring into state j at rateα j . This structure enables the process to jump from one sector of state space to another one (via state 0) with transition rate independent of population size. First, we highlight the difficulties encountered when using standard techniques to construct both time-dependent and equilibrium probabilities. Then we show how to overcome such analytic difficulties by means of a tool developed in Chen and Renshaw (1990, 1993b); this approach is applicable to many processes whose underlying generator on E\{0} has known probability structure. Here we demonstrate the technique through application to the linear birth-death generator on which is superimposed an annihilation/immigration process.

An ontological characterization of time-series and state-sequences for data mining

Time-series and sequences are important patterns in data mining. Based on an ontology of time-elements, this paper presents a formal characterization of time-series and state-sequences, where a state denotes a collection of data whose validation is dependent on time. While a time-series is formalized as a vector of time-elements temporally ordered one after another, a state-sequence is denoted as a list of states correspondingly ordered by a time-series. In general, a time-series and a state-sequence can be incomplete in various ways. This leads to the distinction between complete and incomplete time-series, and between complete and incomplete state-sequences, which allows the expression of both absolute and relative temporal knowledge in data mining.

‘Martial races’ and ‘imperial subjects’: violence and governance in colonial India, 1857–1914

This essay explores the specificity of colonial violence in India. Although imperial and military historians are familiar with several instances of such violence—notably the rebellion in 1857 and the 1919 massacre at the Jallianwalla Bagh in Amritsar—there is a broader, and arguably more significant, history that has largely escaped attention. In contrast to metropolitan European states, where sovereignty derived, at least in principle, from a covenant between subjects and government, the sovereign power of the colonial state was always predicated on the violent subjugation of ‘the natives’. However, while violence was integral to colonialism, such violence was never a purely metropolitan agency: most of those recruited to serve in the colonial military were, themselves, Indian. Exploring the history of the imperial military in South Asia after 1857, the paper outlines the complex and rather ambiguous relationship between the colonial state and its ‘native armies’. RESUME Cet article se penche sur la spe´cificite´ de la violence coloniale. Malgre´ des exemples familiers—comme la grande re´volte de 1857 en Inde ou le massacre de Jallianwalla Bagh a` Amritsar en 1919—il y a une histoire plus large et plus importante qui a e´chappe´e a` l’attention des historiens. Contrairement aux e´tats europe´ens ou la souverainete´ de´rivait en principe du moins d’un contrat social entre les acteurs sociaux, le pouvoir souverain de l’e´tat colonial restait fonde´ sur la subjugation violente des indige`nes.