177,144 research outputs found
The 2010 UK Home Office ‘Sexualisation of Young People’ Review: a discursive policy analysis
No full textThis paper offers a discursive policy analysis of the 2010 UK Home Office Sexualisation of Young People Review, authored by Linda Papadopoulos (2010a). It will scrutinise the narrative presented by the text of the danger posed by cultural representations to healthy development, and trace the way that the text links this danger to catastrophic outcomes: child sexual abuse, exploitation and trafficking. Examining this narrative, the article will propose that the UK Review deploys spatial metaphors to naturalise a gendered account of childhood, sexuality and danger, evoking the creeping influence of a corrupting culture on a girl's most private self. The article will also demonstrate that this spatial narrative underpins the epistemological structure of the text – its separation of the primary from the secondary, the real from the artificial
Franck-Condon simulation of the photoelectron spectrum of SO2- including Duschinsky effects
No full textA theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectrum of the anion SO. Geometry optimizations and harmonic vibrational frequency calculations have been performed on the XA(1) state of SO2 and (XB1)-B-2 state of SO2. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of SO2. The theoretical spectra obtained by employing CCSD(T)/6-31 I+G(2d,p) values are in excellent agreement with the experiment. In addition, the equilibrium geometric parameters, r(c)(OS) = 0.1508 +/- 0.0005 nm and theta(e)(O-S-0) = 113.5 +/- 0.5 degrees, of the (XB1)-B-2 state of SO2, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation. (c) 2005 Elsevier B.V. All rights reserved
Internal conversion rate constant calculations considering Duschinsky, anharmonic and Herzberg-Teller effects
No full textA novel method for calculating rate constants for internal conversion (k(IC)) that simultaneously accounts for Duschinsky, anharmonic and Herzberg-Teller effects has been developed and implemented. This method has been applied to robust planar molecules like tetraoxa[8]circulene (4B), free-base porphyrin (H2P) and pyrometene (PM567) with small Duschinsky rotation (i.e. with almost identical normal coordinates in the ground and excited states) and to poly[n]fluorenes (P[n]F) (n = 2-14) with a substantial Duschinsky rotation. The obtained results show that the Duschinsky effect is large in the harmonic approximation, whereas it is in general much smaller in the anharmonic approximation. The Duschinsky effect is found to be large for high frequency vibrational modes with energies of similar to 3300 cm(-1) such as the X-H (X = C, N and O) stretching modes that mix in the S-1 -> -S-0 electronic transition. However, even in this case, the increase in k(IC) due to the Duschinsky effect does not exceed one order of magnitude. The calculations show that anharmonic contributions to k(IC) are larger than Herzberg-Teller contributions which in turn are larger than contributions from the Duschinsky effect ANH > HT > Du. We also show that an approximation, where only X-H bonds are considered in the k(IC) calculation, is accurate even for P[n]F (n = 2-14).Peer reviewe
Vibronic coupling by two active modes: A simple, exactly solvable model for the Duschinsky effect Vibronic coupling by two active modes: A simple, exactly solvable model for the Duschinsky effect*
No full textThe properties of a simple model for the Duschinsky effect are investigated. The model consists of two electronic states coupled by two harmonic oscillators. Weak and strong adiabatic and nonadiabatic coupling limits are defined. If an alternative phase convention is adopted, the two ways of approaching the strong nonadiabatic coupling limit lead paradoxically, in the one-oscillator case, to adiabatic BornOppenheimer wavefunctions that are exact eigenstates of the system. Expansion of the adiabatic coupling matrix element as a power series in the normal coordinates in the weak nonadiabatic coupling regime is not possible in the two-oscillator case unless a constraint is placed on the Duschinsky parameter
Wait Up!: Attachment and Sovereign Power
No full textSociologists and feminist scholars have, over many decades, characterised attachment as a social construction that functions to support political and gender conservatism. We accept that attachment theory has seen use to these ends and consider recent deployments of attachment theory as justification for a minimal State within conservative political discourse in the UK since 2009. However, we contest that attachment is reducible to its discursive construction. We consider Judith Butler’s depiction of the infant attached to an abusive caregiver as a foundation and parallel to the position of the adult citizen subjected to punitive cultural norms and political institutions. We develop and qualify Butler’s account, drawing on the insights offered by the work of Lauren Berlant. We also return to Foucault’s Psychiatric Power lectures, in which familial relations are situated as an island of sovereign power within the sea of modern disciplinary institutions. These reflections help advance analysis of three important issues: the social and political implications of attachment research; the relationship between disciplinary and sovereign power in the affective dynamic of subjection; and the political and ethical status of professional activity within the psy disciplines
Variations in Duschinsky rotations in m-fluorotoluene and m-chlorotoluene during excitation and ionization
No full textWe investigate Duschinsky rotation/mixing between three vibrations for both m-fluorotoluene (mFT) and m-chlorotoluene (mClT), during electronic excitation and ionization. In the case of mFT, we investigate both the S1 → S0 electronic transition and the D0+ ← S1 ionization, by two-dimensional laser-induced fluorescence (2D-LIF) and zero-electron-kinetic energy (ZEKE) spectroscopy, respectively; for mClT, only the D0+ ← S1 ionization was investigated, by ZEKE spectroscopy. The Duschinsky mixings are different in the two molecules, owing to shifts in vibrational wavenumber and variations in the form of the fundamental vibrations between the different electronic states. There is a very unusual behavior for two of the mFT vibrations, where apparently different conclusions for the identity of two S1 vibrations arise from the 2D-LIF and ZEKE spectra. We compare the experimental observations to the calculated Duschinsky matrices, finding that these successfully pick up the key geometric changes associated with each electronic transition and so are successful in qualitatively explaining the vibrational activity in the spectra. Experimental values for a number of vibrations across the S0, S1, and D0+ states are reported and found to compare well to those calculated. Assignments are made for the observed vibration-torsion (“vibtor”) bands, and the effect of vibrational motion on the torsional potential is briefly discussed
A new method of calculation of Franck-Condon factors which includes allowance for anharmonicity and the Duschinsky effect: Simulation of the HeI photoelectron spectrum of ClO2
No full textA new method of Franck-Condon (FC) factor calculation for nonlinear polyatomics, which includes anharmonicity and Duschinsky rotation, is reported. Watson's Hamiltonian is employed in this method with multidimensional ab initio potential energy functions. The anharmonic vibrational wave functions are expressed as linear combinations of the products of harmonic oscillator functions. The Duschinsky effect, which arises from the rotation of the normal modes of the two electronic states involved in the electronic transition, is formulated in Cartesian coordinates, as was done previously in an earlier harmonic FC model. This new anharmonic FC method was applied to the simulation of the bands in the He I photoelectron (PE) spectrum of ClO2. For the first band, the harmonic FC model was shown to be inadequate but the anharmonic FC simulation gave a much-improved agreement with the observed spectrum. The experimentally derived geometry of the (X) over tilde (1)A(1) state of ClO2+ was obtained, for the first time, via the iterative FC analysis procedure {R(Cl-O)=1.414 +/- 0.002 Angstrom, angle O-Cl-O=121.8 +/- 0.1 degrees}. The heavily overlapped second PE band of ClO2, corresponding to ionization to five cationic states, was simulated using the anharmonic FC code. The main vibrational features observed in the experimental spectrum were adequately accounted for in the simulated spectrum. The spectral simulation reported here supports one of the two sets of published assignments for this band, which was based on multireference configuration interaction (MRCI) calculations. In addition, with the aid of the simulated envelopes, a set of adiabatic (and vertical) ionization energies to all five cationic states involved in this PE band, more reliable than previously reported, has been derived. This led also to a reanalysis of the photoabsorption spectrum of ClO2
Appropriate Similarity Measures for Author Cocitation Analysis
No full textWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Morality, Colour, Bodies: Epistemological and Interpretive Questions of Purity
No full textAs contributors to this special edition show in different ways, purity itself is a less stable concept than may first appear. This insight, however, is not always reflected in dominant theory on the topic. Contributions to this special edition are therefore placed in dialogue with a metanarrative regarding the role of purity in Western history, presented by the influential Harvard sociologist Barrington Moore Jr.. In effect, discussion of Moore’s narrative on purity is a way to expose it differently, allowing the reader to reconsider Moore’s claims. In turn, we hope that the special issue’s contributions will be exposed differently in light of work to refine and redefine Moore’s overarching thesis
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