However, we do not find evidence for truly immobile fractions of water molecules or lithium ions and, hence, for the existence of a static Stern layer in any of the studied silica pores.Functional group substituents are a ubiquitous tool in ground-state organic chemistry often employed to fine-tune chemical properties and obtain desired chemical reaction outcomes. Selleckchem Kinase Inhibitor Library Their effect on photoexcited electronic states, however, remains poorly understood. To help build an intuition for these effects, we have studied ethylene, substituted with electron acceptor (cyano) and/or electron donor (methoxy) substituents, both theoretically and experimentally using ab initio quantum molecular dynamics and time-resolved photoelectron spectroscopy. Our results show the consistent trend that photo-induced ethylenic dynamics is primarily localized to the carbon with the greater electron density. For doubly substituted ethylenes, the trend is additive when both substituents are located on opposite carbons, whereas the methoxy group (in concert with steric effects) dominates when both substituents are located on a single carbon atom. These results point to the development of rules for structure-dynamics correlations; in this case, a novel mechanistic ultrafast photochemistry for conjugated carbon chains employing long-established chemical concepts.The self-assembly of fibrils is a subject of intense interest, primarily due to its relevance to the formation of pathological structures. Some fibrils develop branches via the so-called secondary nucleation. In this paper, we use the master equation approach to model the kinetics of formation of branched fibrils. In our model, a branched fibril consists of one mother branch and several daughter branches. We consider five basic processes of fibril formation, namely, nucleation, elongation, branching, fragmentation, and dissociation of the primary nucleus of fibrils into free monomers. Our main focus is on the effect of the directionality of growth on the kinetics of fibril formation. We consider several cases. At first, the mother branch may elongate from one or from both ends, while the daughter branch elongates only from one end. We also study the case of branched fibrils with bidirectionally growing daughter branches, tangentially to the main stem, which resembles the intertwining process. We derive a set of ordinary differential equations for the moments of the number concentration of fibrils, which can be solved numerically. Assuming that the primary nucleus of fibrils dissociates with the fragmentation rate, in the limit of the zero branching rate, our model reproduces the results of a previous model that considers only the three basic processes of nucleation, elongation, and fragmentation. We also use the experimental parameters for the fibril formation of Huntingtin fragments to investigate the effect of unidirectional vs bidirectional elongation of the filaments on the kinetics of fibrillogenesis.Excited state electron and hole transfer underpin fundamental steps in processes such as exciton dissociation at photovoltaic heterojunctions, photoinduced charge transfer at electrodes, and electron transfer in photosynthetic reaction centers. Diabatic states corresponding to charge or excitation localized species, such as locally excited and charge transfer states, provide a physically intuitive framework to simulate and understand these processes. However, obtaining accurate diabatic states and their couplings from adiabatic electronic states generally leads to inaccurate results when combined with low-tier electronic structure methods, such as time-dependent density functional theory, and exorbitant computational cost when combined with high-level wavefunction-based methods. Here, we introduce a density functional theory (DFT)-based diabatization scheme that directly constructs the diabatic states using absolutely localized molecular orbitals (ALMOs), which we denote as Δ-ALMO(MSDFT2). We demonstrate that our method, which combines ALMO calculations with the ΔSCF technique to construct electronically excited diabatic states and obtains their couplings with charge-transfer states using our MSDFT2 scheme, gives accurate results for excited state electron and hole transfer in both charged and uncharged systems that underlie DNA repair, charge separation in donor-acceptor dyads, chromophore-to-solvent electron transfer, and singlet fission. This framework for the accurate and efficient construction of excited state diabats and evaluation of their couplings directly from DFT thus offers a route to simulate and elucidate photoinduced electron and hole transfer in large disordered systems, such as those encountered in the condensed phase.Silver doping is a valuable route to modulate the structural, electronic, and optical properties of gold clusters. We combine photofragmentation experiments with density functional theory calculations to investigate the relative stability of cationic Ag doped Au clusters, AgAuN-1+ (N ≤ 40). The mass spectra of the clusters after photofragmentation reveal marked drops in the intensity of AgAu8+, AgAu14+, and AgAu34+, indicating a higher relative stability of these sizes. This is confirmed by the calculated AgAuN-1+ (N ≤ 17) dissociation energies peaking for AgAu6+, AgAu8+, and AgAu14+. While the stability of AgAu6+ and AgAu8+ can be explained by the accepted electronic shell model for metal clusters, density of states analysis shows that the geometry plays an important role in the higher relative stability of AgAu14+. For this size, there is a degeneracy lifting of the 1D shell, which opens a relatively large HOMO-LUMO gap with a subshell-closed 1S21P41P21D6 electronic configuration.Two methods for estimating the correlation energy of molecules and other electronic systems are discussed based on the assumption that the correlation energy can be partitioned between atomic regions. In the first method, the electron density is expanded in terms of atomic contributions using rigorous electron repulsion bounds, and in the second method, correlation contributions are associated with basis function pairs. These methods do not consider the detailed nature of localized excitations but instead define a correlation energy per electron factor that is unique to a specific atom. The correlation factors are basis function dependent and are determined by configuration interaction (CI) calculations on diatomic and hydride molecules. The correlation energy estimates are compared with the results of high-level CI calculations for a test set of 27 molecules representing a wide range of bonding environments (average error of 2.6%). An extension based on truncated CI calculations in which d-type and hydrogen p-type functions are eliminated from the virtual space combined with estimates of dynamical correlation contributions using atomic correlation factors is discussed and applied to the dissociation of several molecules.