A Water Stable U(IV) Complex Based on a Macrocyclic Ligand Displaying NIR Emission

Efficient charge-transfer (CT) phosphorescence in the near-IR (NIR) spectral region is reported for four substituted Ru-(R-dipyrrinato) complexes, [Ru(bpy)2(R-dipy)](PF6), where bpy is 2,2'-bipyridine and the substituent R is phenyl (ph), 2,4,6-trimethylphenyl, 4-carboxyphenyl (HOOC-ph), or 4-pyridinyl. The experimentally determined phosphorescence efficiency, ιem(p) = kRAD(p)/(νem(p))3 (where kRAD(p) and νem(p) are the phosphorescence rate constant and the phosphorescence frequency, respectively), of the [Ru(bpy)2(R-dipy)]+ complexes was approximately double that of [Ru(bpy)(Am)4]2+ complexes (Am = ammine ligand) in the NIR region. Density functional theory (DFT) modeling indicated two strikingly different electronic configurations of the triplet emitting state (Te) in the two types of complexes. The Te of [Ru(bpy)2(R-dipy)]+ complexes shows a CT-type corresponding to the metal-to-ligand charge transfer (MLCT)-(Ru-(R-dipy)) and the ππ*-(R-dipy) moiety configurations, and the Te state in the [Ru(bpy)(Am)4]2+ complexes corresponds to an approximately MLCT excited state consisting of mostly MLCT-(Ru-bpy) with a minimal ππ*(bpy) contribution. DFT modeling also indicated that the low-energy singlet excited states in the Te geometry (Sn(T)) of the [Ru(bpy)2(ph-dipy)]+ complex consist of numerous CT-Sn(T)-type states of the Ru-dipy and Ru-bpy moieties, whereas the [Ru(bpy)(Am)4]2+ ions show quite simple MLCT-Sn(T)-type states of the Ru-bpy moiety. Based on experimental observations, DFT modeling, and the plain spin-orbit coupling (SOC) principle, we conclude that the remarkably high ιem(p) amplitudes of the [Ru(bpy)2(R-dipy)]+ complexes relative to those of [Ru(bpy)(Am)4]2+ complexes can be attributed to the relatively substantial contribution of intrinsic SOC-mediated intensity stealing from the numerous low-energy CT-type Sn(T) states.

The terahertz absorption spectra of aspirin and benzoic acid have been measured in the range 200-500 cm-1 (6-15 THz). Density-functional theory (DFT) modeling has assigned fundamental vibrational modes to the observed absorption bands. Hydrogen bonds between the crystalline planes of aspirin resulted in better agreement between the experimental and modeled spectra than for benzoic acid. The similar structure of these two molecules suggests a similar absorption spectrum, which indeed was obtained experimentally. However, the detailed crystal structure and molecular differences result in some of the apparently common absorption bands being assigned to different vibrational modes through the DFT modeling. Thus, our study importantly reveals that even though crystalline forms of two similar molecules may have similar experimental terahertz spectra, the resemblance may be superficial rather than fundamental.

Conspectus Ab initio modeling of matter has become a pillar of chemical research: with ever-increasing computational power, simulations can be used to accurately predict, for example, chemical reaction rates, electronic and mechanical properties of materials, and dynamical properties of liquids. Many competing quantum mechanical methods have been developed over the years that vary in computational cost, accuracy, and scalability: density functional theory (DFT), the workhorse of solid-state electronic structure calculations, features a good compromise between accuracy and speed. However, approximate exchange-correlation functionals limit DFT's ability to treat certain phenomena or states of matter, such as charge-transfer processes or strongly correlated materials. Furthermore, conventional DFT is purely a ground-state theory: electronic excitations are beyond its scope. Excitations in molecules are routinely calculated using time-dependent DFT linear response; however applications to condensed matter are still limited. By contrast, many-electron wavefunction methods aim for a very accurate treatment of electronic exchange and correlation. Unfortunately, the associated computational cost renders treatment of more than a handful of heavy atoms challenging. On the other side of the accuracy spectrum, parametrized approaches like tight-binding can treat millions of atoms. In view of the different (dis-)advantages of each method, the simulation of complex systems seems to force a compromise: one is limited to the most accurate method that can still handle the problem size. For many interesting problems, however, compromise proves insufficient. A possible solution is to break up the system into manageable subsystems that may be treated by different computational methods. The interaction between subsystems may be handled by an embedding formalism. In this Account, we review embedded correlated wavefunction (CW) approaches and some applications. We first discuss our density functional embedding theory, which is formally exact. We show how to determine the embedding potential, which replaces the interaction between subsystems, at the DFT level. CW calculations are performed using a fixed embedding potential, that is, a non-self-consistent embedding scheme. We demonstrate this embedding theory for two challenging electron transfer phenomena: (1) initial oxidation of an aluminum surface and (2) hot-electron-mediated dissociation of hydrogen molecules on a gold surface. In both cases, the interaction between gas molecules and metal surfaces were treated by sophisticated CW techniques, with the remainder of the extended metal surface being treated by DFT. Our embedding approach overcomes the limitations of conventional Kohn-Sham DFT in describing charge transfer, multiconfigurational character, and excited states. From these embedding simulations, we gained important insights into fundamental processes that are crucial aspects of fuel cell catalysis (i.e., O2 reduction at metal surfaces) and plasmon-mediated photocatalysis by metal nanoparticles. Moreover, our findings agree very well with experimental observations, while offering new views into the chemistry. We finally discuss our recently formulated potential-functional embedding theory that provides a seamless, first-principles way to include back-action onto the environment from the embedded region.

Photoluminescence properties and DFT simulations of the Cr ion-implanted (100)-oriented β-Ga2O3 single crystals

This article deals with the spectral analysis of Er3+ and Nd3+ ions doped zinc lithium bismuth borate (ZLiBiB) glasses prepared by melt quenching method. The Vis-NIR absorption spectra of these glasses have been analyzed systematically. Judd-Ofelt intensity parameters Ωλ (λ = 2, 4, 6) have been evaluated and used to compute the radiative properties of emission transitions of Er3+ and Nd3+: ZLiBiB glasses. The NIR emission spectra of Er3+ and Nd3+: ZLiBiB glasses were measured with an Ar+ laser (514.5 nm) as the excitation source. From the NIR emission spectrum of Er3+: ZLiBiB glass a broad emission band centered at 1,538 nm (4I13/2 → 4I15/2) is observed and from Nd3+: ZLiBiB glass, three NIR emission bands at 898, 1,070 and 1,338 nm are observed which are assigned to the transitions (4F3/2 → 4I9/2), (4F3/2 → 4I11/2) and (4F3/2 → 4I13/2) respectively.

Powder synthesis and luminescence of a novel yellow-emitting Ba5Si11Al7N25: Eu2+ phosphor discovered by a single-particle-diagnosis approach for warm w-LEDs

Infrared photodissociation (IR-PD) spectra of iron cluster dinitrogen adsorbate complexes [Fen(N2)m]+ for n = 8-20 reveal slightly redshifted IR active bands in the region of 2200-2340 cm-1. These bands mostly relate to stretching vibrations of end-on coordinated N2 chromophores, a μ1,end end-on binding motif. Density Functional Theory (DFT) modeling and detailed analysis of n = 13 complexes are consistent with an icosahedral Fe13 + core structure. The first adsorbate shell closure at (n,m) = (13,12)-as recognized by the accompanying paper on the kinetics of N2 uptake by cationic iron clusters-comes with extensive IR-PD band broadening resulting from enhanced couplings among adjacent N2 adsorbates. DFT modeling predicts spin quenching by N2 adsorption as evidenced by the shift of the computed spin minima among possible spin states (spin valleys). The IR-PD spectrum of (17,1) surprisingly reveals an absence of any structure but efficient non-resonant fragmentation, which might indicate some weakly bound (roaming) N2 adsorbate. The multiple and broad bands of (17,m) for all other cases than (17,1) and (17,7) indicate a high degree of variation in N2 binding motifs and couplings. In contrast, the (17,7) spectrum of six sharp bands suggests pairwise equivalent N2 adsorbates. The IR-PD spectra of (18,m) reveal additional features in the 2120-2200 cm-1 region, which we associate with a μ1,side side-on motif. Some additional features in the (18,m) spectra at high N2 loads indicate a μ1,tilt tilted end-on adsorption motif.

Site-specific isotope fractionation during Zn adsorption onto birnessite: Insights from X-ray absorption spectroscopy, density functional theory and surface complexation modeling

In situ growth of CuFeS2/CuS bridged heterojunction catalyst with mixed redox-couple cations for excellent photocatalytic degradation of organophosphate insecticide: CFD and DFT modeling

Heavy metals are particularly damaging contaminants in the environment, and even trace concentrations represent a risk to human health due to their toxicity. To detect the heavy metals of Mn2+ and Co2+ ions, a novel selective reusable paper-based Fluorescence naked-eye sensor based on naphthalene cationic Schiff base (NCSB) was synthesized and confirmed using FT-IR, 1 H-NMR, and MS tools. Based on a blue to colorless color change in the aqueous solution, the NCSB sensor is utilized to Mn2+ and Co2+ cations selectively among other metal ions (Fe2+, Cu2+, Mg2+, Ni2+, Zn2+, Cd2+, Hg2+, Pb2+, Sn2+ and Cr3+). In the aqueous medium, the NCSB sensor displayed high sensitivity, with limits of detection (LOD) values of 0.014 µM (14.08 nM) and 0.041 µM (41.47 nM) for Mn2+ and Co2+ cations, respectively. The paper-based sensor naked-eye detected Mn2+ and Co2+ cations in water at concentrations as low as 0.65 µM (65 nM) and 0.086 µM (86 nM), respectively. It was discovered that 5 min of incubation time and a pH range of 7 to 11 were optimal for the complexation reaction between the Mn2+ and Co2+ ions and the NCSB sensor. Through a static quenching process, the interaction of the different metal ions with the Schiff base group in the NCSB molecule results in the development of a ground-state non-fluorescent complex. NCSB sensor was also successfully applied in analysis of Mn2+ and Co2+ in environmental water with good recoveries of 94.8–105.9%. The theoretical calculations based on density functional theory (DFT) studies are in support of experimental interpretations. The links between the input factors and the anticipated response were evaluated using the quadratic model of the response surface methodology (RSM) modeling.Supplementary InformationThe online version contains supplementary material available at 10.1007/s10895-023-03426-6.

Density functional theory (DFT) has been applied to modeling molecular interactions in water for over three decades. The ubiquity of water in chemical and biological processes demands a unified understanding of its physics, from the single molecule to the thermodynamic limit and everything in between. Recent advances in the development of data-driven and machine-learning potentials have accelerated simulation of water and aqueous systems with DFT accuracy. However, anomalous properties of water in the condensed phase, where a rigorous treatment of both local and non-local many-body (MB) interactions is in order, are often unsatisfactory or partially missing in DFT models of water. In this review, we discuss the modeling of water and aqueous systems based on DFT and provide a comprehensive description of a general theoretical/computational framework for the development of data-driven many-body potentials from DFT reference data. This framework, coined MB-DFT, readily enables efficient many-body molecular dynamics (MD) simulations of small molecules, in both gas and condensed phases, while preserving the accuracy of the underlying DFT model. Theoretical considerations are emphasized, including the role that the delocalization error plays in MB-DFT potentials of water and the possibility to elevate DFT and MB-DFT to near-chemical-accuracy through a density-corrected formalism. The development of the MB-DFT framework is described in detail, along with its application in MB-MD simulations and recent extension to the modeling of reactive processes in solution within a quantum mechanics/MB molecular mechanics (QM/MB-MM) scheme, using water as a prototypical solvent. Finally, we identify open challenges and discuss future directions for MB-DFT and QM/MB-MM simulations in condensed phases.

Oxidative dehydrogenation of ethanol on gold: Combination of kinetic experiments and computation approach to unravel the reaction mechanism

ARXPS and DFT studies of thermally induced Pb surface segregation on Au/Cu alloys

Air regulator lockout

Oxidative stress and metal dyshomeostasis are considered crucial factors in the pathogenesis of Alzheimer’s disease (AD). Indeed, transition metal ions such as Cu(II) can generate reactive oxygen species (ROS) via O2 Fenton-like reduction, catalyzed by Cu(II) coordinated to the amyloid-beta (Aβ) peptide. Despite intensive efforts, the mechanisms of ROS-induced molecular damage remain poorly understood. In the present paper, we investigate, on the basis of Density Functional Theory (DFT) computations, a possible mechanism of the OH radical propagation toward membrane phospholipid polar head and fatty acid chains starting from the end-product of the OH radical generation by Cu(II)-Aβ. Using phosphatidylcholine as a model of a single unit inside a membrane, we evaluated the thermochemistry of the OH propagation with the oxidation of a C-H bond and the formation of the radical moiety. The DFT results show that Cu(II)-Aβ-OH can oxidize only sn-2 C-H bonds of the polar head and can easily oxidize the C-H bond adjacent to the carbon–carbon double bond in a mono or bis unsaturated fatty acid chain. These results are discussed on the basis of the recent literature on in vitro Aβ metal-catalyzed oxidation and on the possible implications in the AD oxidative stress mechanism.