Man-Induced Discrete Freshwater Discharge and Changes in Flow Structure and Bottom Turbulence in Altered Yeongsan Estuary, Korea

Flow measurements were performed in the altered Yeongsan estuary, Korea, in August 2011, to investigate changes in flow structure in the water column and turbulence characteristics very close to the bed. Comparison between the bottom turbulent kinetic energy (TKE) and suspended sediment concentration (SSC) was conducted to examine how discrete freshwater discharge affects the bottom sediment concentration. The discrete freshwater discharge due to the gate opening of the Yeongsan estuarine dam induced a strong two-layer circulation: an offshore-flowing surface layer and a landward-flowing bottom layer. The fine flow structure from the bed to 0.35 m above the bottom (mab hereafter) exhibited an upside-down-bell-shaped profile for which current speed was nearly uniform above 0.1 mab, with the magnitude of the horizontal and vertical flow speeds reaching 0.1 and 0.01 m/s, respectively. The bottom turbulence responded to the freshwater discharge at the surface layer and the maximum magnitude of the Reynolds stress reached up to 2 × 10−4 m2/s2 during the discharged period, which coincided with increased SSC in the bottom boundary layer. These results indicate that the surface freshwater discharge due to opening of the estuarine dam gate increases the SSC by the discharge-induced intensification of the turbulent flow in the bottom boundary layer

Reactivity of molecular oxygen with aluminum clusters: Density functional and Ab Initio molecular dynamics simulation study

Dissociative adsorption of molecular oxygen (O-2) on aluminum (Al) clusters has attracted much interest in the field of surface science and catalysis, but theoretical predictions of the reactivity of this reaction in terms of barrier height is still challenging. In this regard, we systematically investigate the reactivity of O-2 with Al clusters using density functional theory (DFT) and atom-centered density matrix propagation (ADMP) simulations. We also calculate potential energy surfaces (PESs) of the reaction between O-2 and Al clusters to estimate the barrier energy of this reaction. The M06-2X functional gives the barrier energy in agreement with the one calculated by coupled cluster singles and doubles with perturbed triples (CCSD(T)) while the TPSSh functional significantly underestimates the barrier height. The ADMP simulation using the M06-2X functional predicts the reactivity of O-2 with the Al cluster in agreement with the experimental findings, that is, singlet O-2 readily reacts with Al clusters but triplet O-2 is less reactive. We found that the ability of a DFT functional to describe the charge transfer appropriately is critical for calculating the barrier energy and the reactivity of the reaction of O-2 with Al clusters. The M06-2X functional is relevant for investigating chemical reactions involving Al and O-2. (c) 2016 Wiley Periodicals, Inc.11Nsciescopu

Density Functional Theory Assessment of Molecular Structures and Energies of Neutral and Anionic Al_<i>n</i> (<i>n</i> = 2–10) Clusters

We report the results of a benchmarking study on hybrid, hybrid-meta, long-range-corrected, meta-generalized gradient approximation (meta-GGA), and GGA density functional theory (DFT) methods for aluminum (Al) clusters. A range of DFT functionals, such as B3LYP, B1B95, PBE0, mPW1PW91, M06, M06-2X, ωB97X, ωB97XD, TPSSh, BLYP, PBE, mPWPW91, M06-L, and TPSS, have been used to optimize the molecular structures and calculate the vibrational frequencies and four energetic parameters for neutral and anionic Al_<i>n</i> (<i>n</i> = 2–10) clusters. The performances of these functionals are assessed systematically by calculating the vertical ionization energy for neutral Al clusters and the vertical electron detachment energy for anionic Al clusters, along with the cohesive energy and dissociation energy. The results are compared with the available experimental and high-level ab initio calculated results. The calculated results showed that the PBE0 and mPW1PW91 functionals generally provide better results than the other functionals studied. TPSS can be a good choice for the calculations of very large Al clusters. On the other hand, the B3LYP, BLYP, and M06-L functionals are in poor agreement with the available experimental and theoretical results. The calculated results suggest that the hybrid DFT functionals like B3LYP do not always provide better performance than GGA functionals

Femtosecond Soft X-ray Spectroscopy of Solvated Transition-Metal Complexes : Deciphering the Interplay of Electronic and Structural Dynamics

We present the first implementation of femtosecond soft X-ray spectroscopy as an ultrafast direct probe of the excited-state valence orbitals in solution phase molecules. This method is applied to photoinduced spin crossover of [Fe(tren(py)(3))](2+), where the ultrafast spin state conversion of the metal ion, initiated by metal-to-ligand charge transfer excitation, is directly measured using the intrinsic spin state selectivity of the soft X-ray L-edge transitions. Our results provide important experimental data concerning the mechanism of ultrafast spin state conversion and subsequent electronic and structural dynamics, highlighting the potential of this technique to study ultrafast phenomena in the solution phase

Solvatochromic and Ligand Effects in Ultrafast Intramolecular Electron Transfer in Fe-based Molecular Photosensitizers

Metal-to-ligand charge-transfer (MLCT) excited state lifetimes of [Fe(CN)4(2,2’-bipyridine)]2- and [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2-exhibit strong solvent and ligand dependence. We conclude that these effects can be described with Marcus-like model where changes in the MLCT energy correspond directly to the changes in the electron transfer driving force and all the other factors (e.g. reorganization energy) can be considered constant

Solvatochromic and Ligand Effects in Ultrafast Intramolecular Electron Transfer in Fe-based Molecular Photosensitizers

Metal-to-ligand charge-transfer (MLCT) excited state lifetimes of [Fe(CN)4(2,2’-bipyridine)]2- and [Fe(CN)4(2,3-bis(2-pyridyl)pyrazine)]2-exhibit strong solvent and ligand dependence. We conclude that these effects can be described with Marcus-like model where changes in the MLCT energy correspond directly to the changes in the electron transfer driving force and all the other factors (e.g. reorganization energy) can be considered constant

Tracking reaction dynamics in solution by pump–probe X-ray absorption spectroscopy and X-ray liquidography (solution scattering)

Characterization of transient molecular structures formed during chemical and biological processes is essential for understanding their mechanisms and functions. Over the last decade, time-resolved X-ray liquidography (TRXL) and time-resolved X-ray absorption spectroscopy (TRXAS) have emerged as powerful techniques for molecular and electronic structural analysis of photoinduced reactions in the solution phase. Both techniques make use of a pump–probe scheme that consists of (1) an optical pump pulse to initiate a photoinduced process and (2) an X-ray probe pulse to monitor changes in the molecular structure as a function of time delay between pump and probe pulses. TRXL is sensitive to changes in the global molecular structure and therefore can be used to elucidate structural changes of reacting solute molecules as well as the collective response of solvent molecules. On the other hand, TRXAS can be used to probe changes in both local geometrical and electronic structures of specific X-ray-absorbing atoms due to the element-specific nature of core-level transitions. These techniques are complementary to each other and a combination of the two methods will enhance the capability of accurately obtaining structural changes induced by photoexcitation. Here we review the principles of TRXL and TRXAS and present recent application examples of the two methods for studying chemical and biological processes in solution. Furthermore, we briefly discuss the prospect of using X-ray free electron lasers for the two techniques, which will allow us to keep track of structural dynamics on femtosecond time scales in various solution-phase molecular reactions

Time-Resolved X‑ray Spectroscopy in the Water Window: Elucidating Transient Valence Charge Distributions in an Aqueous Fe(II) Complex

Time-resolved nitrogen-1s spectroscopy in the X-ray water window is presented as a novel probe of metal–ligand interactions and transient states in nitrogen-containing organic compounds. New information on iron­(II) polypyridyl complexes via nitrogen core-level transitions yields insight into the charge density of the photoinduced high-spin state by comparing experimental results with time-dependent density functional theory. In the transient high-spin state, the 3d electrons of the metal center are more delocalized over the nearest-neighbor nitrogen atoms despite increased bond lengths. Our findings point to a strong coupling of electronic states with charge-transfer character, facilitating the ultrafast intersystem crossing cascade in these systems. The study also highlights the importance of local charge density measures to complement chemical interaction concepts of charge donation and back-bonding with molecular orbital descriptions of states