Photodissociation Dynamics of OCS near 214 nm Using Ion Imaging

The OCS photodissociation dynamics of the dominant S(1 D 2) channel near 214 nm have been studied using velocity map ion imaging. We report a CO vibrational branching ratio of 0.79:0.21 for v = 0:v = 1, indicating substantially higher vibrational excitation than that observed at slightly longer wavelengths. The CO rotational distribution is bimodal for both v = 0 and v = 1, although the bimodality is less pronounced than at longer wavelengths. Vector correlations, including rotational alignment, indicate that absorption to both the 21A′ (A) and 11A″ (B) states is important in the lower-j part of the rotational distribution, while only 21A′ state absorption contributes to the upper part; this conclusion is consistent with work at longer wavelengths. Classical trajectory calculations including surface hopping reproduce the measured CO rotational distributions and their dependence on wavelength well, though they underestimate the v = 1 population. The calculations indicate that the higher-j peak in the rotational distribution arises from molecules that begin on the 21A′ state but make nonadiabatic transitions to the 11A′ (X) state during the dissociation, while the lower-j peak arises from direct photodissociation on either the 21A′ or the 11A″ states, as found in previous work

Nascent O\u3csub\u3e2\u3c/sub\u3e (a\u3csup\u3e1\u3c/sup\u3eΔ\u3csub\u3eg\u3c/sub\u3e, v = 0, 1) Rotational Distributions from the Photodissociation of Jet‐Cooled O\u3csub\u3e3\u3c/sub\u3e in the Hartley Band

We report rotational distributions for the O2 (a 1Δg) fragment from photodissociation of jet‐cooled O3 at 248, 266, and 282 nm. The rotational distributions show a population alternation that favors the even states, as previously reported for a 300 K sample by Valentini et al. (J. Chem. Phys. 86, 6745 (1987)). The alternation from the jet‐cooled precursor is much stronger than that observed by Valentini et al., and in contrast to their observations does not depend strongly on O2 (a 1Δg) vibrational state or photolysis wavelength. The odd/even alternation diminishes substantially when the ozone beam temperature is increased from 60 to 200 K, confirming its dependence on parent internal energy. The magnitude of the even/odd alternation in product rotational states from the cold ozone sample, its temperature dependence, and other experimental and theoretical evidence reported since 1987 suggest that the alternation originates from a Λ‐doublet propensity, and not from a mass independent curve crossing effect as previously proposed

An examination of business occupier relocation decision making : distinguishing small and large firm behaviour

This paper explores how business occupiers decide whether and where to relocate. It captures the experience and behaviour of a range of sizes and types of business occupier and subjects their decision-making processes to detailed scrutiny. A linear three-stage decision model is used to sequence and structure interviews with individuals who have intimate involvement with the relocation of 28 firms and organizations in Tyne and Wear, in the north-east of England. The 'constant comparative' method is used to analyse the interview data, from which emerges 18 key concepts, comprising 51 characteristic components. Using an axial approach, these are organized into 10 cross-cutting themes that represent the main areas of consideration or influence on the thinking of the people involved in determining whether a firm or organization should relocate and, if so, where to. The resulting analysis finds that organizations adopt varying degrees of sophistication when making relocation decisions; small firms are more inclined to make decisions based on constrained information; larger organizations adopt a more complex approach. Regardless of firm size, key individuals exert considerable influence over the decision-making process and its outcome

Loss of ACTN3 gene function alters mouse muscle metabolism and shows evidence of positive selection in humans

More than a billion humans worldwide are predicted to be completely deficient in the fast skeletal muscle fiber protein α-actinin-3 owing to homozygosity for a premature stop codon polymorphism, R577X, in the ACTN3 gene. The R577X polymorphism is associ

Power, norms and institutional change in the European Union: the protection of the free movement of goods

How do institutions of the European Union change? Using an institutionalist approach, this article highlights the interplay between power, cognitive limits, and the normative order that underpins institutional settings and assesses their impact upon the process of institutional change. Empirical evidence from recent attempts to reinforce the protection of the free movement of goods in the EU suggests that, under conditions of uncertainty, actors with ambiguous preferences assess attempts at institutional change on the basis of the historically defined normative order which holds a given institutional structure together. Hence, path dependent and incremental change occurs even when more ambitious and functionally superior proposals are on offer

The role of triplet states in the long wavelength absorption region of bromine nitrate

A theoretical study of the low-lying singlet and triplet electronic states of BrONO 2 is presented. Calculations of excitation energies and oscillator strengths are reported using excited-state coupled cluster response methods, as well as the complete active space self-consistent field method with the full Breit-Pauli spin-orbit operator. The calculations predict that there is only one singlet state for BrONO 2 , the à 1 AЉ state, that is accessible at wavelengths longer than 300 nm. At energies below the first singlet state, i.e., Ͼ330 nm, the calculations reveal two triplet states with significant oscillator strength. Therefore, we propose that the origin of absorption in the long wavelength region from 350 to 500 nm, responsible for the majority of atmospheric photolysis, is due to transitions to triplet states and not singlet states. A comparison of the reported benchmark coupled cluster calculations ͑CCSD͒ with the results of ͑1͒ configuration interaction with all single substitutions and a perturbative correction for the double substitutions ͓CIS͑D͔͒ and ͑2͒ time-dependent density-functional ͑TDDF͒ calculations is provided. For the lowest energy excitations, CIS͑D͒ calculations provide quantitative agreement with the CCSD results, while TDDF calculations yield qualitative agreement

Different paths to the modern state in Europe: the interaction between domestic political economy and interstate competition

Theoretical work on state formation and capacity has focused mostly on early modern Europe and on the experience of western European states during this period. While a number of European states monopolized domestic tax collection and achieved gains in state capacity during the early modern era, for others revenues stagnated or even declined, and these variations motivated alternative hypotheses for determinants of fiscal and state capacity. In this study we test the basic hypotheses in the existing literature making use of the large date set we have compiled for all of the leading states across the continent. We find strong empirical support for two prevailing threads in the literature, arguing respectively that interstate wars and changes in economic structure towards an urbanized economy had positive fiscal impact. Regarding the main point of contention in the theoretical literature, whether it was representative or authoritarian political regimes that facilitated the gains in fiscal capacity, we do not find conclusive evidence that one performed better than the other. Instead, the empirical evidence we have gathered lends supports to the hypothesis that when under pressure of war, the fiscal performance of representative regimes was better in the more urbanized-commercial economies and the fiscal performance of authoritarian regimes was better in rural-agrarian economie

The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation