Geometric and Electronic Effects in the Binding Affinity of Imidazole-Based N-Heterocyclic Carbenes to Cu(100)- and Ag(100)-Based Pd and Pt Single-Atom Alloy Surfaces.

We have conducted nonlocal periodic density functional theory (DFT) calculations of N-heterocyclic carbenes (NHCs) adsorbed to Pd/Cu(100), Pt/Cu(100), Pd/Ag(100), and Pt/Ag(100) single atom alloys (SAAs) utilizing the nonlocal optPBE-vdW functional. NHCs with electron donating groups (EDGs) are predicted to bind more strongly to the SAA surface compared to NHCs functionalized with electron withdrawing groups (EWGs). Our calculations show that NHCs typically bind to SAA geometries containing a small space between the heteroatom sites for the SAAs considered. Generally, this pattern is predicted to persist for a single NHCs or for a pair of NHCs bound to the SAA surfaces. Approximate linear relationships between NMR-based parameters and NHC-SAA binding energies are uncovered. We predict that the binding of NHCs to SAA surfaces is composition-dependent and heteroatom geometry dependent.

Coupled local mode method for simulating vibrational spectroscopy.

Experimental and theoretical studies have highlighted protonated water clusters (PWCs) as important models of the excess proton in aqueous systems. A significant focus has been characterizing the spectral signatures associated with different excess proton solvation motifs. Accurate vibrational frequency calculations are crucial for connecting the measured spectra to the structure of PWCs. In this paper, we extend and characterize a coupled local mode (CLM) approach for calculating the infrared spectra of PWCs using the H+(H2O)4 cluster as a benchmark system. The CLM method is relatively low cost and incorporates the anharmonicity and coupling of OH vibrations. Here, we demonstrate the accuracy of the technique compared to experiments. We also illustrate the dependence of calculated spectral features on the underlying electronic structure theory and basis sets used in the local mode frequency and coupling calculations.

Coupled Local-Mode Approach for the Calculation of Vibrational Spectra: Application to Protonated Water Clusters.

Spectroscopic studies of protonated water clusters (PWCs) have yielded enormous insights into the fundamental nature of the hydrated proton. Here, we introduce a new coupled local-mode (CLM) approach to calculate PWC OH stretch vibrational spectra. The CLM method combines a sampling of representative configurations from density functional theory (DFT)-based ab initio molecular dynamics (AIMD) simulations with DFT calculations of local-mode vibrational frequencies and couplings. Calculations of inhomogeneous OH stretch vibrational spectra for H+(H2O)4 and H+(H2O)21 agree well with experiment and higher-level calculations, and decompositions of the calculated spectra in terms of the coupled modes aids in the interpretation of the spectra. This observation is consistent with the idea that capturing anharmonicity and coupling is as important to accuracy as the underlying level of electronic structure theory. The CLM calculations can easily discern the configuration that dominates the experimental measurement for H+(H2O)5, which can adopt several low-energy conformations.

Revisiting ring-degenerate rearrangements of 1-substituted-4-imino-1,2,3-triazoles.

The 1-substituted-4-imino-1,2,3-triazole motif is an established component of coordination compounds and bioactive molecules, but depending on the substituent identity, it can be inherently unstable due to Dimroth rearrangements. This study examined parameters governing the ring-degenerate rearrangement reactions of 1-substituted-4-imino-1,2,3-triazoles, expanding on trends first observed by L'abbé et al. The efficiency of condensation between 4-formyltriazole and amine reactants as well as the propensity of imine products towards rearrangement was each strongly influenced by the substituent identity. It was observed that unsymmetrical condensation reactions conducted at 70 °C produced up to four imine products via a dynamic equilibrium of condensation, rearrangement and hydrolysis steps. Kinetic studies utilizing 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde with varying amines showed rearrangement rates sensitive to both steric and electronic factors. Such measurements were facilitated by a high throughput colorimetric assay to directly monitor the generation of a 4-nitroaniline byproduct.

Do Format Differences in the Presentation of Information Affect Susceptibility to Memory Distortions? The Three-Stage Misinformation Procedure Reconsidered.

To date most studies within the misinformation paradigm have used the visual presentation of a to-be-remembered event that is later tested verbally or visually. However, the well-established encoding specificity hypothesis predicts that congruence between encoding and test phases should lead to fewer memory errors. In Study 1, we examined the susceptibility to misinformation after encoding original information in 1 of 4 different formats: as a film, slides, and as a written or auditory narrative. All participants were tested verbally, and those who encoded original information pictorially (as a video or slides) were more likely to incorrectly accept verbally suggested information. This might be-a consequence of encoding-retrieval format match. In Study 2, using either verbal or pictorial modality during encoding, postevent information, and test (fully crossed design), we partially supported the encoding-retrieval format match hypothesis; however, auditory presentation of original or postevent information modified the effect, showing that a memory trace created after auditory description was the strongest.