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Objective: Some exonerees receive compensation and aid after being exonerated of their wrongful convictions, and some do not. Looking beyond differences in state statutes, we examined possible reasons for biases in receiving compensation (via statutes or civil claims) and other reintegration services. More specifically, we examined how two unique types of false admission of guilt (i.e., false confessions and false guilty pleas) could be associated with biased outcomes in compensation procurement and reintegration outcomes., Hypotheses: Although we did not have formal hypotheses for this qualitative study, based on the cumulative disadvantage framework (Scherr, Redlich, & Kassin, 2020), we anticipated that both types of false admission of guilt would negatively bias exonerees' experience post-exoneration. More specifically, we expected that exonerees whose cases involved at least one type of false admission of guilt would have a more difficult time obtaining compensation and would experience more negative post-exoneration outcomes, compared with exonerees in general., Method: We conducted in-depth interviews with three samples: (a) exonerees ( n = 19), (b) attorneys who had assisted exonerees with post-exoneration compensation claims ( n = 15), and (c) innocence advocates who had worked with exonerees ( n = 9)., Results: Across all samples, interviewees indicated that both forms of false admission of guilt are associated with biases that may influence exonerees' compensation and reintegration efforts. Specifically, interviews revealed that (a) false admissions are associated with disadvantages to exonerees' compensation and reintegration efforts, as predicted by the cumulative disadvantage framework; (b) under specific circumstances, false admissions are associated with advantages benefiting compensation attempts; and (c) false admissions can be nonapplicable (i.e., irrelevant) to reintegration efforts., Conclusions: Together, our findings provide a more nuanced understanding of the role false confessions and false guilty pleas may play post-exoneration. This understanding, derived from those individuals directly involved in the compensation and reintegration processes, is an important step in beginning to right the injustices experienced by those wrongfully convicted. (PsycInfo Database Record (c) 2024 APA, all rights reserved).

Background: False confessions are often the product of an interrogation process, and the method by which an interrogation is conducted likely affects both the rate of truthful confessions and false confessions. An optimal interrogation method will maximize the former and minimize the latter., Objectives: The current study was a partial update and extension of Meissner and colleagues' (2012) prior Campbell systematic review titled Interview and Interrogation Methods and their Effects on True and False Confessions . Our objective was to assess the effects of interrogation approach on the rates of true and false confessions for criminal (mock) suspects., Search Methods: PsycINFO, Criminal Justice Abstracts, and 15 other databases were searched starting October 20, 2022, with the final search conducted on May 23, 2023; together with reference checking, citation searching, and contact with authors to identify additional studies., Selection Criteria: All eligible studies experimentally manipulated interrogation approach (i.e., accusatorial, information-gathering, or direct questioning) were conducted with mock suspects accused of wrongdoing where ground truth was known, and included information about confession rates., Data Collection and Analysis: We used standard methodological procedures expected by The Campbell Collaboration for our selection of studies and data collection. However, we developed our own risk of bias items and analyzed our data using network meta-analysis methods. Data were synthesized via random-effects network meta-analysis based on the logged odds ratio., Main Results: Across the 27 research articles that provided statistical information sufficient to calculate an effect size, 29 individual studies provided a total of 81 effect sizes. Most studies were conducted with college students in the United States. Overall, our risk of bias assessment indicated that authors generally adhered to double-blind procedures and avoided selective reporting of outcomes. Of note, however, it was often unclear how violations of the randomization process were dealt with.For true confessions, there were 12 studies estimating the effect between accusatorial and direct questioning, five estimating the effect between information-gathering and direct questioning, and another five estimating the effect between accusatorial and information-gathering. Compared to information-gathering, on average, the accusatorial conditions observed fewer true confessions, although not statistically significant (combined OR = 0.55, 95% CI 0.29, 1.05). The largest effects were between information-gathering and direct questioning, with the former producing significantly more true confessions on average (combined OR = 2.43, 95% CI 1.29, 4.59). This model showed good consistency between the direct and indirect effects.For false confessions, there were 20 studies estimating the effect between accusatorial and direct questioning, 4 studies estimating the effect between information-gathering and direct questioning, and 7 estimating the effect between accusatorial and information-gathering. On average, accusatorial conditions yielded more false confessions than direct questioning (combined OR = 3.03, 95% CI 1.83, 5.02) or information-gathering (combined OR = 4.41, 95% CI 1.77, 10.97), both of which are statistically significant. In contrast, direct questioning and information-gathering had roughly similar rates of false confessions with nonsignificant and small effects that slightly favored information-gathering (combined OR = 0.69, 95% CI 0.27, 1.78). This model showed good consistency between the direct and indirect effects.For true confessions under a six-node model, most of the direct, indirect, and combined network estimated mean odds ratios were not statistically significant. The only significant effects were for (1) information-gathering versus direct questioning, with the former resulting in more true confessions (combined OR = 2.57, 95% CI 1.38, 4.78); and (2) accusatorial-evidence ploy versus information-gathering with the former resulting in fewer true confessions (combined OR = 0.37, 95% CI 0.16, 0.84).For false confessions under a six-node model, we found significant effects for (1) accusatorial-evidence ploys versus direct questioning, with the former resulting in more false confessions (combined OR = 2.98, 95% CI 1.59, 5.59); (2) accusatorial-evidence ploys versus information-gathering, with the former resulting in more false confessions (combined OR = 4.47, 95% CI 1.46, 13.68); (3) accusatorial-other versus direct questioning, with the former resulting in more false confessions (combined OR = 3.12, 95% CI 1.37, 7.10); (4) accusatorial-other versus information-gathering, with the former resulting in more false confessions (combined OR = 4.67, 95% CI 1.61, 13.55); and (5) information-gathering versus minimization, with the latter resulting in more false confessions (combined OR = 0.25, 95% CI = 0.08, 0.83). No other combined effects were significant. This model should be interpreted cautiously, however, as the Q statistics raised concerns regarding model consistency., Authors' Conclusions: Overall, results support calls for reforming policies related to interviewing and interrogation practices to prohibit the use of accusatorial approaches and require the adoption of approaches that are science-based., (© 2024 The Author(s). Campbell Systematic Reviews published by John Wiley & Sons Ltd on behalf of The Campbell Collaboration.)

Mechanochemistry has experienced a renaissance in recent years witnessing, at the molecular level, a remarkable interplay between theory and experiment. Molecular mechanochemistry has welcomed a broad spectrum of quantum-chemical methods to evaluate the influence of an external mechanical force on molecular properties. In this contribution, an overview is given on recent work on quantum mechanochemistry in the Brussels Quantum Chemistry group (ALGC). The effect of an external force was scrutinized both in fundamental topics, like reactivity descriptors in Conceptual DFT, and in applied topics, such as designing molecular force probes and tuning the stereoselectivity of certain types of reactions. In the conceptual part, a brief overview of the techniques introducing mechanical forces into a quantum-mechanical description of a molecule is followed by an introduction to conceptual DFT. The evolution of the electronic chemical potential (or electronegativity), chemical hardness and electrophilicity are investigated when a chemical bond in a series of diatomics is put under mechanical stress. Its counterpart, the influence of mechanical stress on bond angles, is analyzed by varying the strain present in alkyne triple bonds by applying a bending force, taking the strain promoted alkyne-azide coupling cycloaddition as an example. The increase of reactivity of the alkyne upon bending is probed by Fukui functions and the local softness. In the applied part, a new molecular force probe is presented based on an intramolecular 6π-electrocyclization in constrained polyenes operating under thermal conditions. A cyclic process is conceived where ring opening and closure are triggered by applying or removing an external pulling force. The efficiency of mechanical activation strongly depends on the magnitude of the applied force and the distance between the pulling points. The idea of pulling point distances as a tool to identify new mechanochemical processes is then tested in [28]hexaphyrins with an intricate equilibrium between Möbius aromatic and Hückel antiaromatic topologies. A mechanical force is shown to trigger the interconversion between the two topologies, using the distance matrix as a guide to select appropriate pulling points. In a final application, the Felkin-Anh model for the addition of nucleophiles to chiral carbonyls under the presence of an external mechanical force is scrutinized. By applying a force for restricting the conformational freedom of the chiral ketone, otherwise inaccessible reaction pathways are promoted on the force-modified potential energy surfaces resulting in a diastereoselectivity different from the force-free reaction.

This is the protocol for a Campbell systematic review. The objective is to assess the effects of interrogation approach on confession outcomes for criminal (mock) suspects., (© 2023 The Authors. Campbell Systematic Reviews published by John Wiley & Sons Ltd on behalf of The Campbell Collaboration.)

Anti-Felkin-Anh diastereoselectivity can be achieved for nucleophilic additions to α-chiral ketones upon stretching the ketone with a mechanical pulling force. Herein, a mechanochemical Felkin-Anh model is proposed for predicting the outcome of a nucleophilic addition to an α-chiral ketone. Essentially, the fully stretched chiral ketone has one substituent shielding each side of the carbonyl, in contrast to the Felkin-Anh model, in which free rotation around a bond is required to achieve the two rotamers of the ketone. Depending on the pulling scenario, either Felkin-Anh or anti-Felkin-Anh diastereoselectivity is obtained. The model is entirely based on the distance between the pulling points, which is maximized in the anti-periplanar arrangement. The major diastereomer is associated with the approach with the least steric interactions. The intuitive model is validated by means of mechanochemical density functional theory calculations. Importantly, the ketone is fully stretched in the sub 1 nN force regime, thus minimizing the risk of undesired homolytic bond rupture. Moreover, the mechanical force is not used for lowering the reaction barriers associated with the nucleophilic addition; instead, it is solely applied for locking the conformation of a molecule and provoking otherwise inaccessible reaction pathways on the force-modified potential energy surface.

Non-covalent π-π stacking interactions often play a key role in the stability of the secondary and tertiary structures of peptides and proteins, respectively, and can be a means of ensuring the binding of ligands within protein and enzyme binding sites. It is generally accepted that minor structural changes to the aromatic ring, such as substitution, can have a large influence on these interactions. Nevertheless, a thorough understanding of underpinning phenomena guiding these key interactions is still limited. This is especially true for larger aromatic structures. To expand upon this knowledge, elaborate ab initio calculations were performed to investigate the effect of halogenation on the stability of 3-methylindole stacking. 3-Methylindole served as a representation of the tryptophan side chain, and is a frequently used motif in drug design and development. Moreover, an expression is derived that is able to accurately predict the interaction stability of stacked halogenated 3-methylindole dimers as well as halogenated toluene dimers, based on monomer level calculated DFT descriptors. We aim for this expression to provide the field with a straightforward and reliable method to assess the effect of halogenation on the π-π stacking interactions between aromatic scaffolds.

The conjugated π-system in polyenes can be interrupted by electrocyclic ring-closure reactions. In this work, this 6π-electrocylization is shown by means of density functional calculations to be reversible by the application of an external mechanical pulling force at the terminal ends of the interrupted polyene chain. The test systems were constrained in a fused ring system, thus locking the orientation of three π-bonds and generally promoting 6π-electrocyclic ring-closure reactions. For several systems, the forward reaction is exergonic and the corresponding reaction barrier is comparable to those reported in the literature. The reverse reaction is triggered by an external pulling force of 2 nN (nano-Newton) or less and also becomes exergonic in all investigated polyenes under these force conditions. Moreover, it proceeds via a low reaction barrier when a pulling force of 2 nN is active, indicating that the mechanical force is an efficient stimulus for triggering ring-opening reactions. Analysis of the strain energy induced by this mechanical force confirms an optimal activation of the corresponding C-C σ-bond that breaks upon ring opening when the pulling positions are located on the polyene chain.

A hitherto unexplored class of molecules for molecular force probe applications are expanded porphyrins. This work proves that mechanical force is an effective stimulus to trigger the interconversion between Hückel and Möbius topologies in [28]hexaphyrin, making these expanded porphyrins suitable to act as conformational mechanophores operating at mild (sub-1 nN) force conditions. A straightforward approach based on distance matrices is proposed for the selection of pulling scenarios that promote either the planar Hückel topology or the three lowest lying Möbius topologies. This approach is supported by quantum mechanochemical calculations. Force distribution analyses reveal that [28]hexaphyrin selectively allocates the external mechanical energy to molecular regions that trigger Hückel-Möbius interconversions, explaining why certain pulling scenarios favor the Hückel two-sided topology and others favor Möbius single-sided topologies. The meso-substitution pattern on [28]hexaphyrin determines whether the energy difference between the different topologies can be overcome by mechanical activation., (© 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Following the recent discovery of stable octa-coordinated alkaline earth metals with N 2 and CO, the role of group II metals in the catalytic reduction of these ligands by means of density functional theory (DFT) calculations and conceptual DFT-based reactivity indices is investigated. Cubic group IV and octahedral group VI transition metal complexes as well as the free ligands are computed for reference. The outer and most accessible atoms of N 2 and CO become much more nucleophilic and electrophilic in all complexes, relevant for N 2 fixation, as probed by the Fukui function and local softness. Within one row of the periodic table, the alkaline earth complexes often show the strongest activation. On the contrary, the electrostatic character is found to be virtually unaffected by complexation. Trends in the soft frontier orbital and hard electrostatic character are in agreement with calculated proton affinities and energy decomposition analyses of the protonated structures, demonstrating the dominance of the soft (HOMO-LUMO) orbital interactions., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

The ability to understand and predict ambident reactivity is key to the rational design of organic syntheses. An approach to understand trends in ambident reactivity is the hard and soft acids and bases (HSAB) principle. The recent controversy over the general validity of this principle prompted us to investigate the competing gas-phase S N 2 reaction channels of archetypal ambident nucleophiles CN - , OCN - , and SCN - with CH 3 Cl (S N 2@C) and SiH 3 Cl (S N 2@Si), using DFT calculations. Our combined analyses highlight the inability of the HSAB principle to correctly predict the reactivity trends of these simple, model reactions. Instead, we have successfully traced reactivity trends to the canonical orbital-interaction mechanism and the resulting nucleophile-substrate interaction energy. The HOMO-LUMO orbital interactions set the trend in both S N 2@C and S N 2@Si reactions. We provide simple rules for predicting the ambident reactivity of nucleophiles based on our Kohn-Sham molecular orbital analysis., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

In our effort to implement the mechanical force used to activate single molecules in mechanochemistry in the context of conceptual density functional theory, we present a theoretical investigation of strained alkynes for rationalizing structural trends as well as the reactivity of cyclic alkynes that are of great importance in in vivo click reactions. The strain on the triple bond in cyclic alkynes is modeled by angular constraints in a 2-butyne fragment and the corresponding bending force is calculated by means of an extended COGEF (constrained geometries simulate external forces) model. In general, the force required to bend the triple bond is smaller with electron-withdrawing groups on the propargylic C-atom, which elegantly results in smaller angles around the triple bond in cyclic alkynes with such substitution pattern. By means of conceptual DFT descriptors, the electrophilic and nucleophilic character of bent triple bonds was investigated revealing moderate activation for small distortions from the linear geometry (0° to 15°) and a drastically more reactive π-space if the triple bond is bent further. This analysis of the intrinsic reactivity of the triple bond is in line with experimental observations, explaining the reactive nature of cyclooctynes and cycloheptynes, whereas larger cyclic systems do not drastically activate the triple bond., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

In molecular mechanochemistry, the chemical properties of a reactant system are modified through the absorption of mechanical energy at the single molecular level, as opposed to thermochemistry (heat), electrochemistry (electrical current) and photochemistry (light). In this proof-of-concept paper, we present a theoretical approach to rationalize and predict the change in chemical properties and concepts when an external stretching force, Fext, is applied to a chemical bond. By considering perturbations to the total molecular energy due to Fext, a series of mechanochemical response indices are obtained within the framework of conceptual density functional theory (DFT). Trends in these indices monitoring the change in hardness and electrophilicity among others, were rationalized for a number of diatomic molecules in terms of the ground-state geometry and the frontier molecular orbitals of the molecule. Finally, we present a set of rules that can be easily adopted for polyatomic molecules to predict the changing chemical reactivity of single molecules when subjected to an external force.