Elucidating solvent contributions to solution reactions with ab initio QM/MM methods.

Computer simulations of reaction processes in solution in general rely on the definition of a reaction coordinate and the determination of the thermodynamic changes of the system along the reaction coordinate. The reaction coordinate often is constituted of characteristic geometrical properties of the reactive solute species, while the contributions of solvent molecules are implicitly included in the thermodynamics of the solute degrees of freedoms. However, solvent dynamics can provide the driving force for the reaction process, and in such cases explicit description of the solvent contribution in the free energy of the reaction process becomes necessary. We report here a method that can be used to analyze the solvent contributions to the reaction activation free energies from the combined QM/MM minimum free-energy path simulations. The method was applied to the self-exchange S(N)2 reaction of CH(3)Cl + Cl(-), showing that the importance of solvent-solute interactions to the reaction process. The results were further discussed in the context of coupling between solvent and solute molecules in reaction processes.

Reformulating time-dependent density functional theory with non-orthogonal localized molecular orbitals.

Time-dependent density functional theory (TDDFT) has broad application in the study of electronic response, excitation and transport. To extend such application to large and complex systems, we develop a reformulation of TDDFT equations in terms of non-orthogonal localized molecular orbitals (NOLMOs). NOLMO is the most localized representation of electronic degrees of freedom and has been used in ground state calculations. In atomic orbital (AO) representation, the sparsity of NOLMO is transferred to the coefficient matrix of molecular orbitals (MOs). Its novel use in TDDFT here leads to a very simple form of time propagation equations which can be solved with linear-scaling effort. We have tested the method for several long-chain saturated and conjugated molecular systems within the self-consistent charge density-functional tight-binding method (SCC-DFTB) and demonstrated its accuracy. This opens up pathways for TDDFT applications to large bio- and nano-systems.

Event memory: A theory of memory for laboratory, autobiographical, and fictional events.

An event memory is a mental construction of a scene recalled as a single occurrence. It therefore requires the hippocampus and ventral visual stream needed for all scene construction. The construction need not come with a sense of reliving or be made by a participant in the event, and it can be a summary of occurrences from more than one encoding. The mental construction, or physical rendering, of any scene must be done from a specific location and time; this introduces a "self" located in space and time, which is a necessary, but need not be a sufficient, condition for a sense of reliving. We base our theory on scene construction rather than reliving because this allows the integration of many literatures and because there is more accumulated knowledge about scene construction's phenomenology, behavior, and neural basis. Event memory differs from episodic memory in that it does not conflate the independent dimensions of whether or not a memory is relived, is about the self, is recalled voluntarily, or is based on a single encoding with whether it is recalled as a single occurrence of a scene. Thus, we argue that event memory provides a clearer contrast to semantic memory, which also can be about the self, be recalled voluntarily, and be from a unique encoding; allows for a more comprehensive dimensional account of the structure of explicit memory; and better accounts for laboratory and real-world behavioral and neural results, including those from neuropsychology and neuroimaging, than does episodic memory.

Ghost and self: Jung's paradigm shift and a response to Zinkin

Zinkin's lucid challenge to Jung makes perfect sense. Indeed, it is the implications of this `making sense' that this paper addresses. For Zinkin's characterization of the `self' takes it as a `concept' requiring coherence; a variety of abstract non-contextual knowledge that itself has a mythical heritage. Moreover, Zinkin's refinement of Jung seeks to make his work fit for the scientific paradigm of modernity. In turn, modernity's paradigm owes much to Newton's notion of knowledge via reductionism. Here knowledge or investigation is divided up into the smallest possible units with the aim of eventually putting it all together into `one' picture of scientific truth. Unfortunately, `reductionism' does not do justice to the resonant possibilities of Jung's writing. These look forward to a new scientific paradigm of the twenty-first century, of the interactive `field', emergence and complexity theory. The paper works paradoxically by discovering Zinkin's `intersubjective self' after all, in two undervalued narratives by Jung, his doctoral thesis and a short late ghost story. However, in the ambivalences and radical fictional experimentation of these fascinating texts can be discerned an-Other self, one both created and found. [From the Publisher]

Adult personality inconsistency and problems with parents: uncovering the roots of the false self

Research has established that individuals who tend to vary their personality depending on who they are with, show a variety of signs of psychological maladjustment in comparison to those who do not; they show more negative affect (Baird, Le and Lucas, 2006), lower life satisfaction (Suh, 2002), lower self-esteem (Sheldon et al., 1997), lower role-satisfaction (Donahue et al., 1993), higher rates of depression (Lutz and Ross, 2003), more anxiety (Diehl, Hastings and Stanton, 2001) and poorer physical health (Cross, Gore and Morris, 2003). It has also been shown that personality variability is positively related to the experience of inauthenticity and falsity (Sheldon et al., 1997). Donahue, Roberts, Robins and John (1993) found that personality inconsistency of this type is related to tension within the family. Psychoanalytic theory has also linked the operation of an adult false self to experiences with parents, particularly in early life (Winnicott, 1960). It was hypothesized that personality variability and the adult experience of falsity in social situations would be related to an emotionally unstable relationship with parents. The method to test this comprised a questionnaire-based survey given to a non-clinical population. The final sample comprised 305, with 193 women and 112 men, aged from 19 to 55. The first questionnaire asked participants to rate personality traits, including emotional stability, in three social contexts - with parents, with friends and with work colleagues. The second part involved 3 questions; participants were asked to select in which of the aforementioned three social contexts they felt “most themselves”; in which they were “most authentic” and in which they “put on a front”. It was found, consistent with predictions, that an index of overall personality variability calculated from the personality questionnaire correlated strongly with emotional instability around parents (r = 0.46, p<0.001), while not correlating with emotional instability in either of the other two contexts measured. This suggests a specific link between a person’s relationship with their parents and their overall personality integration. Furthermore, it was found that participants who cited one of the three social contexts (parents, friends, work colleagues) as being one in which they were “more themselves” or “more authentic” had significantly higher ratings of emotional instability with parents than those participants who found that they were equally authentic across settings (F = 9.8, p<0.005). The results suggest a clear link between a person’s relationships with their parents and their adult personality integration. An explanation is that individuals who experience an anxious or ambiguous attachment with their parents in childhood may fear rejection or abandonment in later life, and so habitually adapt their personality to fit in to social contexts as adults, in order to be accepted by others and to minimize the possibility of social rejection. These individuals meanwhile retain an emotionally unstable relationship with their parents in adulthood. This interpretation is speculative but is open to empirical testing. Clinicians should be aware that attachment problems with parents may underlie poor personality integration in adulthood.

To fit in or stand out? The interaction between mortality salience, dissent and self esteem on social projection

Social projection (SP) refers to our tendency to assume that others think the same as we do, but the effect can also be used to detect the extent to which participants want to see themselves as similar to others. Simon et al (1997) found that participants informed that they were deviant increased their SP but those told that they were conformist reduced theirs. This compensatory function supports Brewer’s optimal distinctiveness which states that a balance must be struck between competing desires to feel similar and unique. In line with terror management theory, the effect was particularly apparent under conditions of mortality salience (MS). So far SP has only been examined on measures that target personal identity so this experiment developed a measure to target social identity as well. Participants were provided with either minority or majority dissent feedback, in MS or control conditions, and their SP on items relevant to personal and social identity were recorded. Results showed that group feedback only impacted upon participants SP on social identity measures and interacted with MS and self-esteem; those with high self-esteem had higher SP scores following minority dissent under conditions of mortality salience, indicating an attempt to assert their individuality. On SP measures targeting personal identity, MS and self-esteem interacted; the death prime increased SP scores for those with low self-esteem but decreased it for those with high self-esteem. Findings are interpreted in terms of TMT and optimal distinctiveness theory and their applications.

Implications of streamlining theory for microbial ecology

Whether a small cell, a small genome or a minimal set of chemical reactions with self-replicating properties, simplicity is beguiling. As Leonardo da Vinci reportedly said, 'simplicity is the ultimate sophistication'. Two diverging views of simplicity have emerged in accounts of symbiotic and commensal bacteria and cosmopolitan free-living bacteria with small genomes. The small genomes of obligate insect endosymbionts have been attributed to genetic drift caused by small effective population sizes (Ne). In contrast, streamlining theory attributes small cells and genomes to selection for efficient use of nutrients in populations where Ne is large and nutrients limit growth. Regardless of the cause of genome reduction, lost coding potential eventually dictates loss of function. Consequences of reductive evolution in streamlined organisms include atypical patterns of prototrophy and the absence of common regulatory systems, which have been linked to difficulty in culturing these cells. Recent evidence from metagenomics suggests that streamlining is commonplace, may broadly explain the phenomenon of the uncultured microbial majority, and might also explain the highly interdependent (connected) behavior of many microbial ecosystems. Streamlining theory is belied by the observation that many successful bacteria are large cells with complex genomes. To fully appreciate streamlining, we must look to the life histories and adaptive strategies of cells, which impose minimum requirements for complexity that vary with niche.

Explaining binge drinking among adolescent males using the Theory of Planned Behaviour

Binge drinking among adolescents in Northern Ireland is prevalent and has detrimental eff ects on public health. Health education interventions, based on valid explanatory models of health behaviour, are required to reduce binge drinking behaviour among adolescents. " is paper examines the utility of the " eory of Planned Behaviour in explaining binge drinking behaviour among adolescent males. Using questionnaire responses from 94 adolescent boys attending secondary schools in the Belfast area, logistic regression modelling suggested that the " eory of Planned Behaviour explained 36% of the variance in self-reported binge drinking behaviour. Attitudes towards binge drinking were the strongest predictor of binge drinking behaviour. Tackling attitudes about binge drinking is a challenge to be considered when designing interventions to reduce binge drinking among this population

A Density Functional Theory Study on the Active Center of Fe-Only Hydrogenase: Characterization and Electronic Structure of the Redox States

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z) (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fed at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(l) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(l)-Fe(l) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride, Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(l) species, but cannot bond with the Fe(l)-Fe(l) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (1) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(l)-Fe(l) complexes; and (iii) in the e(g)-2pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

Analogies between linguistics and information theory

An analogy is established between the syntagm and paradigm from Saussurean linguistics and the message and messages for selection from the information theory initiated by Claude Shannon. The analogy is pursued both as an end itself and for its analytic value in understanding patterns of retrieval from full text systems. The multivalency of individual words when isolated from their syntagm is contrasted with the relative stability of meaning of multi-word sequences, when searching ordinary written discourse. The syntagm is understood as the linear sequence of oral and written language. Saussureâ??s understanding of the word, as a unit which compels recognition by the mind, is endorsed, although not regarded as final. The lesser multivalency of multi-word sequences is understood as the greater determination of signification by the extended syntagm. The paradigm is primarily understood as the network of associations a word acquires when considered apart from the syntagm. The restriction of information theory to expression or signals, and its focus on the combinatorial aspects of the message, is sustained. The message in the model of communication in information theory can include sequences of written language. Shannonâ??s understanding of the written word, as a cohesive group of letters, with strong internal statistical influences, is added to the Saussurean conception. Sequences of more than one word are regarded as weakly correlated concatenations of cohesive units.

Theory of the near K-edge structure in electron energy loss spectroscopy

Arguments are given that lead to a formalism for calculating near K-edge structure in electron energy loss spectroscopy (EELS). This is essentially a one electron picture, while many body effects may be introduced at different levels, such as the local density approximation to density functional theory or the GW approximation to the electron self-energy. Calculations are made within the all electron LMTO scheme in crystals with complex atomic and electronic structures, and these are compared with experiment. (c) 2004 Elsevier B.V. All rights reserved.

Emission-line ratios for [N II] in gaseous nebulae and a comparison between theory and observation

R-matrix calculations of electron impact excitation rates among the 2s(2)2p(2) P-3, D-1, S-1, and 2s2p(3) S-5 levels of N II are presented. These results are used in conjunction with other recent calculations of electron impact excitation rates and Einstein A-coefficients for N II to derive the emission-line ratio: ratio diagrams and where (R-1, R-2) (R-1, R-3), where R-1 = I(5756.2 Angstrom)/I(6549.9 + 6585.2 Angstrom), R-2 = I(2143.5 Angstrom)/I(6549.9 + 6585.2 Angstrom), and R-3 = I(2139.7 Angstrom)/I(6549.9 + 658.2 Angstrom), for a range of electron temperatures (T-e = 5000-20,000 K) and electron densities (N-e = 10(2)-10(7) cm(-3)) appropriate to gaseous nebulae. These diagrams should, in principle, allow the simultaneous determination of T-e and N-e from measurements of the [N II] lines in a spectrum. Plasma parameters deduced for a sample of gaseous nebulae, using observational data obtained from ground-based telescopes plus the International Ultraviolet Explorer and Hubble Space Telescope satellites, are found to show generally excellent internal consistency and to be in good agreement with the values of T-e and N-e estimated from other line ratios. These results provide observational support for the accuracy of the theoretical ratios and hence the atomic data adopted in their derivation. Theoretical ratios are also presented for the infrared line pair R-4 = I(122 mum)/I(205 mum), and the usefulness of R-4 as an electron density diagnostic is briefly discussed.

Electro-thermal theory of intermodulation distortion in lossy microwave components

An analytic formulation of dynamic electro-thermally induced nonlinearity is developed for a general resistive element, yielding a self-heating circuit model based on a fractional derivative. The model explains the 10 dB/decade slope of the intermodulation products observed in two-tone testing. Two-tone testing at 400 MHz of attenuators, microwave chip terminations, and coaxial terminations is reported with tone spacing ranging from 1 to 100 Hz.

Beyond homo economicus: Recognition, self-realization and social work

This paper builds on Ferguson's important contribution to the debate on personalization in social work that appeared in the British Journal of Social Work in 2007. Whereas Ferguson approached the topic through the lens of political philosophy, the account below draws on critical social theory to examine not only the nature of personalization, but also its supportive pillar of individualization. In particular, Axel Honneth's critique of individualization in modern society is presented before setting out his ideas on the need for self-realization through inter-subjective recognition. The implications of Honneth's position are then considered in terms of four interrelated dimensions of social work practice, namely: (i) social work as symbolic interaction; (ii) social work as care; (iii) social work as respect; and (iv) social work as validation. It is argued that this constellation of practices poses a direct and necessary challenge to a social work of personalization.