Investigating Emotionality: Psychology, Aesthetics, and the Global Mental Health Crisis

A Cultural Approach to Emotional Disorders. Psychological and Aesthetic Interpretations von E. Deidre Pribram setzt sich mit einer Vielzahl von Themen auseinander, wie beispielsweise der psychologischen Selbst-Konzeptionen und der Figur des verrückten Genies oder medizinischer Diagnostik und neurologischer Forschung. Die Autorin trägt dabei zur Analyse der globalen Krise der psychischen Gesundheit und der Untersuchung des Verhältnisses zwischen Psy-Disziplinen und ästhetischer Praxis bei und beleuchtet darüber hinaus auf einer allgemeineren Ebene das Potential von Kulturtheorien in der Betrachtung von Emotionen.A Cultural Approach to Emotional Disorders. Psychological and Aesthetic Interpretations by E. Deidre Pribram investigates a wide range of topics, such as the psychological conception of self and the figure of the mad genius or medical diagnostics and neurological research. It thus not only contributes to the analysis of what is commonly referred to as the global mental health crisis or an inquiry into the relationship between the psy disciplines and aesthetic practice, but also – on a broader level – examines the potential of cultural theory in the study of emotions

Charge-transfer in time-dependent density-functional theory via spin-symmetry-breaking

Long-range charge-transfer excitations pose a major challenge for time-dependent density functional approximations. We show that spin-symmetry-breaking offers a simple solution for molecules composed of open-shell fragments, yielding accurate excitations at large separations when the acceptor effectively contains one active electron. Unrestricted exact-exchange and self-interaction-corrected functionals are performed on one-dimensional models and the real LiH molecule within the pseudopotential approximation to demonstrate our results.Comment: 5 pages, 4 figure

Use of 15N NMR spectroscopy to probe covalency in a thorium nitride.

Reaction of the thorium metallacycle, [Th{N(R)(SiMe2)CH2}(NR2)2] (R = SiMe3) with 1 equiv. of NaNH2 in THF, in the presence of 18-crown-6, results in formation of the bridged thorium nitride complex, [Na(18-crown-6)(Et2O)][(R2N)3Th(μ-N)(Th(NR2)3] ([Na][1]), which can be isolated in 66% yield after work-up. Complex [Na][1] is the first isolable molecular thorium nitride complex. Mechanistic studies suggest that the first step of the reaction is deprotonation of [Th{N(R)(SiMe2)CH2}(NR2)2] by NaNH2, which results in formation of the thorium bis(metallacycle) complex, [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)], and NH3. NH3 then reacts with unreacted [Th{N(R)(SiMe2)CH2}(NR2)2], forming [Th(NR2)3(NH2)] (2), which protonates [Na(THF) x ][Th{N(R)(SiMe2CH2)}2(NR2)] to give [Na][1]. Consistent with hypothesis, addition of excess NH3 to a THF solution of [Th{N(R)(SiMe2)CH2}(NR2)2] results in formation of [Th(NR2)3(NH2)] (2), which can be isolated in 51% yield after work-up. Furthermore, reaction of [K(DME)][Th{N(R)(SiMe2CH2)}2(NR2)] with 2, in THF-d 8, results in clean formation of [K][1], according to 1H NMR spectroscopy. The electronic structures of [1]- and 2 were investigated by 15N NMR spectroscopy and DFT calculations. This analysis reveals that the Th-Nnitride bond in [1]- features more covalency and a greater degree of bond multiplicity than the Th-NH2 bond in 2. Similarly, our analysis indicates a greater degree of covalency in [1]- vs. comparable thorium imido and oxo complexes

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations.

Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded a protonated ligand [L(H)]+ and hydroxide [ML2(OH)]2+ or hydrate [ML(L-H)(H2O)]2+, where (L-H)- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+ and for both product isomers, [ML2(OH)]2+ and [ML(L-H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+-L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding

Crystal Field in Rare-Earth Complexes:From Electrostatics to Bonding

The flexibility of first-principles (ab initio) calculations with the SO-CASSCF (complete active space self-consistent field theory with a treatment of the spin-orbit (SO) coupling by state interaction) method is used to quantify the electrostatic and covalent contributions to crystal field parameters. Two types of systems are chosen for illustration: 1)The ionic and experimentally well-characterized PrCl3 crystal; this study permits a revisitation of the partition of contributions proposed in the early days of crystal field theory; and 2)a series of sandwich molecules [Ln(ηn-CnHn)2]q, with Ln=Dy, Ho, Er, and Tm and n=5, 6, and 8, in which the interaction between LnIII and the aromatic ligands is more difficult to describe within an electrostatic approach. It is shown that a model with three layers of charges reproduces the electrostatic field generated by the ligands and that the covalency plays a qualitative role. The one-electron character of crystal field theory is discussed and shown to be valuable, although it is not completely quantitative. This permits a reduction of the many-electron problem to a discussion of the energy of the seven 4f orbitals

Giant spin-orbit effects on H-1 and C-13 NMR shifts for uranium(VI) complexes revisited: role of the exchange-correlation response kernel, bonding analyses, and new predictions

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Previous relativistic quantum-chemical predictions of unusually large H-1 and C-13 NMR chemical shifts for ligand atoms directly bonded to a diamagnetic uranium(VI) center (P. Hrobarik, V. Hrobarikova, A. H. Greif and M. Kaupp, Angew. Chem., Int. Ed., 2012, 51, 10884) have been revisited by two- and four-component relativistic density functional methods. In particular, the effect of the exchange-correlation response kernel, which had been missing in the previously used two-component version of the Amsterdam Density Functional program, has been examined. Kernel contributions are large for cases with large spin-orbit (SO) contributions to the NMR shifts and may amount to up to similar to 30% of the total shifts, which means more than a 50 ppm difference for the metal-bonded carbon shifts in some extreme cases. Previous calculations with a PBE-40HF functional had provided overall reasonable predictions, due to cancellation of errors between the missing kernel contributions and the enhanced exact-exchange (EXX) admixture of 40%. In the presence of an exchange-correlation kernel, functionals with lower EXX admixtures give already good agreement with experiments, and the PBE0 functional provides reasonable predictive quality. Most importantly, the revised approach still predicts unprecedented giant H-1 NMR shifts between +30 ppm and more than +200 ppm for uranium(VI) hydride species. We also predict uranium-bonded C-13 NMR shifts for some synthetically known organometallic U(VI) complexes, for which no corresponding signals have been detected to date. In several cases, the experimental lack of these signals may be attributed to unexpected spectral regions in which some of the C-13 NMR shifts can appear, sometimes beyond the usual measurement area. An extremely large uranium-bonded C-13 shift above 550 ppm, near the upper end of the diamagnetic C-13 shift range, is predicted for a known pincer carbene complex. Bonding analyses allow in particular the magnitude of the SO shifts, and of their dependence on the functional, on the ligand position in the complex, and on the overall electronic structure to be better appreciated, and improved confidence ranges for predicted shifts have been obtained