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83 ± 0.15 T) is measured to be very close to the respective theoretical value, and it shows that the surface oxide layers do not affect the magnetic moments in NWs. Our results provide a useful synthesis approach for the fabrication of single-crystalline, defect-free metal NWs and give insight into the micromagnetic properties in ferromagnetic NWs based on the transmission electron microscopy measurements.The degradation of fibrils under the influence of thermal fluctuations was studied experimentally by various groups around the world. In the first set of experiments, it was shown that the decay of fibril content, which can be measured by the ThT fluorescence assay, obeys a bi-exponential function. In the second series of experiments, it was demonstrated that when the monomers separated from the aggregate are not recyclable, the time dependence of the number of monomers belonging to the dominant cluster is described by a single-exponential function if the fraction of bound chains becomes less than a certain threshold. Note that the time dependence of the fraction of bound chains can be measured by tryptophan fluorescence. To understand these interesting experimental results, we developed a phenomenological theory and performed molecular simulation. According to our theory and simulations using the lattice and all-atom models, the time dependence of bound chains is described by a logistic function, which slowly decreases at short time scales but becomes a single exponential function at large time scales. The results, obtained by using lattice and all-atom simulations, ascertained that the time dependence of the fibril content can be described by a bi-exponential function that decays faster than the logistic function on short time scales. We have uncovered the molecular mechanism for the distinction between the logistic and bi-exponential behavior. Since the dissociation of the chain from the fibrils requires the breaking of a greater number of inter-chain contacts as compared to the breaking of the beta sheet structure, the decrease in the number of connected chains is slower than the fibril content. Therefore, the time dependence of the aggregate size is logistic, while the two-exponential behavior is preserved for the content of fibrils. Our results are in agreement with the results obtained in both sets of experiments.Solvent polarization around a polar solute molecule plays an essential role in determining the electronic and thermodynamic properties of solutions. In this study, a solvent-polarizable model in response to solute polarization is proposed, which is coupled with a three-dimensional reference interaction-site model theory. The charge-response kernel is used to describe solvent polarizability, and four different coupling schemes are assessed. The most feasible behavior scheme among them is the one that incorporates responses not only to solute polarization but also to solute-induced solvent polarization. The numerical results indicated that solvent molecules near the polar solute show significant polarization, and therefore, the model proposed here is useful for considering the solvation process and thermodynamics of polar solute molecules.We present a framework for the calculation of diabatic states using the combined density functional theory and multireference configuration interaction (DFT/MRCI) method. Due to restrictions present in the current formulation of the DFT/MRCI method (a lack of analytical derivative couplings and the inability to use non-canonical Kohn-Sham orbitals), most common diabatization strategies are not applicable. We demonstrate, however, that diabatic wavefunctions and potentials can be reliably calculated at the DFT/MRCI level of theory using a propagative variant of the block diagonalization diabatization method (P-BDD). The proposed procedure is validated via the calculation of diabatic potentials for LiH and the simulation of the vibronic spectrum of pyrazine. In both cases, the combination of the DFT/MRCI and P-BDD methods is found to correctly recover the non-adiabatic coupling effects of the problem.In this work, we present a combined experimental and theoretical study on the V L2,3-edge x-ray absorption (XAS) and x-ray magnetic circular dichroism (XMCD) spectra of VIVO(acac)2 and VIII(acac)3 prototype complexes. The recorded V L2,3-edge XAS and XMCD spectra are richly featured in both V L3 and L2 spectral regions. In an effort to predict and interpret the nature of the experimentally observed spectral features, a first-principles approach for the simultaneous prediction of XAS and XMCD spectra in the framework of wavefunction based ab initio methods is presented. The theory used here has previously been formulated for predicting optical absorption and MCD spectra. In the present context, it is applied to the prediction of the V L2,3-edge XAS and XMCD spectra of the VIVO(acac)2 and VIII(acac)3 complexes. In this approach, the spin-free Hamiltonian is computed on the basis of the complete active space configuration interaction (CASCI) in conjunction with second order N-electron valence state perturbation the basis of a generalized state coupling mechanism based on the type of the excitations dominating the relativistically corrected states. In the second step, the performance of CASCI, CASCI/NEVPT2, and ROCIS/DFT is evaluated. The very good agreement between theory and experiment has allowed us to unravel the complicated XMCD C-term mechanism on the basis of the SOC interaction between the various multiplets with spin S' = S, S ± 1. In the last step, it is shown that the commonly used spin and orbital sum rules are inadequate in interpreting the intensity mechanism of the XAS and XMCD spectra of the VIVO(acac)2 and VIII(acac)3 complexes as they breakdown when they are employed to predict their magneto-optical properties. This conclusion is expected to hold more generally.Determining the multi-reference character of a molecular system and its impact on the limits within which its properties may be calculated accurately by different quantum chemical methods remains a difficult yet important task in computational chemistry. Especially, transition metal compounds continue to frequently provide a challenge to quantum chemists in this regard. In this work, we construct, analyze, and evaluate different computational protocols to determine the impact of the multi-reference character of transition metal compounds on their bond dissociation energies using a set of reference data for 60 diatomic molecules. We find that the fractional orbital density approach allows to determine two global indicators on a physically sound basis. These can subsequently be used to classify the assessed set of molecules with high accuracy into categories of systems for which their multi-reference character matters substantially for their bond dissociation energies and for which it does not. A comparison with earlier suggested thresholds for classification of molecular systems due to their multi-reference character suggests that our approaches yield substantially better performance.Wide bandgap oxides can be sensitized to visible light by coupling them with plasmonic nanoparticles (NPs). We investigate the optical and electronic properties of composite materials made of Ag NPs embedded within cerium oxide layers of different thickness. The electronic properties of the materials are investigated by x-ray and ultraviolet photoemission spectroscopy, which demonstrates the occurrence of static charge transfers between the metal and the oxide and its dependence on the NP size. Ultraviolet-visible spectrophotometry measurements show that the materials have a strong absorption in the visible range induced by the excitation of localized surface plasmon resonances. The plasmonic absorption band can be modified in shape and intensity by changing the NP aspect ratio and density and the thickness of the cerium oxide film.The acetonyl radical (•CH2COCH3) is relevant to atmospheric and combustion chemistry due to its prevalence in many important reaction mechanisms. One such reaction mechanism is the decomposition of Criegee intermediates in the atmosphere that can produce acetonyl radical and OH. In order to understand the fate of the acetonyl radical in these environments and to create more accurate kinetics models, we have examined the reaction system of the acetonyl radical with O2 using highly reliable theoretical methods. Structures were optimized using coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] with an atomic natural orbital (ANO0) basis set. Energetics were computed to chemical accuracy using the focal point approach involving perturbative treatment of quadruple excitations [CCSDT(Q)] and basis sets as large as cc-pV5Z. The addition of O2 to the acetonyl radical produces the acetonylperoxy radical, and multireference computations on this reaction suggest it to be barrierless. No submerged pathways were found for the unimolecular isomerization of the acetonylperoxy radical. Besides dissociation to reactants, the lowest energy pathway available for the acetonylperoxy radical is a 1-5 H shift from the methyl group to the peroxy group through a transition state that is 3.3 kcal mol-1 higher in energy than acetonyl radical + O2. The ultimate products from this pathway are the enol tautomer of the acetonyl radical along with O2. Multiple pathways that lead to OH formation are considered; however, all of these pathways are predicted to be energetically inaccessible, except at high temperatures.This perspective addresses the development of polymer field theory for predicting the equilibrium phase behavior of block polymer melts. The approach is tailored to the high-molecular-weight limit, where universality reduces all systems to the standard Gaussian chain model, an incompressible melt of elastic threads interacting by contact forces. Using mathematical identities, this particle-based version of the model is converted to an equivalent field-based version that depends on fields rather than particle coordinates. The statistical mechanics of the field-based model is typically solved using the saddle-point approximation of self-consistent field theory (SCFT), which equates to mean field theory, but it can also be evaluated using field theoretic simulations (FTS). While SCFT has matured into one of the most successful theories in soft condensed matter, FTS are still in its infancy. The two main obstacles of FTS are the high computational cost and the occurrence of an ultraviolet divergence, but fortunately there has been recent groundbreaking progress on both fronts. As such, FTS are now well poised to become the method of choice for predicting fluctuation corrections to mean field theory.In this manuscript, we examine the role of image charge effects on the electrostatic potential fluctuations experienced by ionic species in the vicinity of an electrode surface. We combine simulation and theory to quantify these fluctuations and how they vary with distance from the electrode surface. We observe that the potential distribution narrows significantly for species within a few electrolyte screening lengths of the electrode. We attribute this narrowing to the effects of image charge fluctuations originating from the polarization response of the electrode. We show that the physical consequences of these image charge effects can be captured in the context of a simple analytical field theory with anti-symmetric boundary conditions. We contextualize these results by discussing their implications for rates of Marcus-like outer-sphere interfacial electron transfer.