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Computational quantum chemistry can be more than just numerical experiments when methods are specifically adapted to investigate chemical concepts. One important example is the development of energy decomposition analysis (EDA) to reveal the physical driving forces behind intermolecular interactions. In EDA, typically the interaction energy from a good-quality density functional theory (DFT) calculation is decomposed into multiple additive components that unveil permanent and induced electrostatics, Pauli repulsion, dispersion, and charge-transfer contributions to noncovalent interactions. Herein, we formulate, implement, and investigate decomposing the forces associated with intermolecular interactions into the same components. The resulting force decomposition analysis (FDA) is potentially useful as a complement to the EDA to understand chemistry, while also providing far more information than an EDA for data analysis purposes such as training physics-based force fields. We apply the FDA based on absolutely localized molecular orbitals (ALMOs) to analyze interactions of water with sodium and chloride ions as well as in the water dimer. We also analyze the forces responsible for geometric changes in carbon dioxide upon adsorption onto (and activation by) gold and silver anions. We also investigate how the force components of an EDA-based force field for water clusters, namely MB-UCB, compare to those from force decomposition analysis.

Oxidation states represent the ionic distribution of charge in a molecule and are significant in tracking redox reactions and understanding chemical bonding. While effective algorithms already exist based on formal Lewis structures as well as using localized orbitals, they exhibit differences in challenging cases where effects such as redox noninnocence are at play. Given a density functional theory (DFT) calculation with chosen total charge and spin multiplicity, this work reports a new approach to obtaining fragment-localized orbitals that is termed oxidation state localized orbitals (OSLO), together with an algorithm for assigning the oxidation state using the OSLOs and an associated fragment orbital localization index (FOLI). Evaluating the FOLI requires fragment populations, and for this purpose a new version of the intrinsic atomic orbital (IAO) scheme is introduced in which the IAOs are evaluated using a reference minimal basis formed from on-the-fly superposition of atomic density (IAO-AutoSAD) calculations in the target basis set and at the target level of theory. The OSLO algorithm is applied to a range of challenging cases including high valent metal oxide complexes, redox noninnocent NO and dithiolate transition metal complexes, a range of carbene-containing TM complexes, and other examples including the potentially inverted ligand field in [Cu(CF3)4]-. Across this range of cases, OSLO produces generally satisfactory results. Furthermore, in borderline cases, the OSLOs and associated FOLI values provide direct evidence of the emergence of covalent interactions between fragments that nicely complements existing approaches.

The oxidation state (OS) of metals and ligands in inorganic complexes may be defined by carefully curated rules, such as from IUPAC, or by computational procedures such as the effective oxidation state (EOS) or localized orbital bonding analysis (LOBA). Such definitions typically agree for systems with simple ionic bonding and innocent ligands but may disagree as the boundary between ionic and covalent bonds is approached, or as the role of ligand noninnocence becomes nontrivial, or high oxidation states of metals are supported by heavy dative bonding, and so on. This work systematically compares IUPAC, EOS, and LOBA across a series of complexes where OS assignment is challenging. These systems include high-valent transition metal oxides, transition metal complexes with noninnocent ligands such as dithiolate and nitrosyl, metal sulfur dioxide adducts, and two transition metal carbene complexes. The differences in OS assignment by the three methods are carefully discussed, demonstrating the synergy between EOS and LOBA. In addition, a clarity index for LOBA OS assignments is introduced that provides an indication of whether or not its predictions are close to the ionic-covalent boundary.

Atmospheric pollution caused by aerosols deteriorates air quality, increasing public health risks. Anthropogenic aerosols are usually located within the atmospheric boundary layer (ABL), which presents a daytime evolution that determines the air pollutants' vertical mixing of those produced near the surface and, therefore, their ground-level concentration from local sources. Precise and complete characterization of the mixing layer is of crucial importance for numerical weather forecasting and climate models, but traditional methods such as radiosounding present some spatial and temporal limitations. Better resolutions have been obtained using lidar, which provides the aerosol vertical distribution. A particular type of lidar, the ceilometer, has demonstrated continuous measurement capabilities, providing vertical profiles with sub-minute time resolution and several-meter spatial resolution. Advanced methods, such as the recently developed STRATfinder algorithm, are required to estimate the ABL height in the presence of residual layers. More complex situations occur due to the advection of aerosols (e.g., due to long-range transport of desert dust, volcanic eruptions, or pyrocloud convection), producing a lofted layer in the free troposphere that may remain decoupled from the local ABL but can also be mixed. Aerosol-based methods for determination of the ABL height are challenging in those situations. The main objective of this research is the assessment of the impact of Saharan dust intrusions on the ABL using ceilometer signals, over a period of four years, 2020–2023. The ABL height database, obtained from ceilometer measurements every hour, is analyzed based on the most frequent synoptic patterns. A reduction in the ABL height was obtained from high dust load days (1576 ± 876 m) with respect to low dust load days (1857 ± 914 m), although it was still higher than clean days (1423 ± 772 m). This behavior is further studied discriminating by season and synoptic patterns. These results are relevant for health advice during Saharan dust intrusion days. [ABSTRACT FROM AUTHOR]

In the so-called Interacting Quantum Atoms (IQA) approach, the molecular energy is numerically decomposed as a sum of atomic and diatomic contributions. While proper formulations have been put forward for both Hartree–Fock and post-Hartree–Fock wavefunctions, this is not the case for the Kohn–Sham density functional theory (KS-DFT). In this work, we critically analyze the performance of two fully additive approaches for the IQA decomposition of the KS-DFT energy, namely, the one from Francisco et al., which uses atomic scaling factors, and that from Salvador and Mayer based upon the bond order density (SM-IQA). Atomic and diatomic exchange–correlation (xc) energy components are obtained for a molecular test set comprising different bond types and multiplicities and along the reaction coordinate of a Diels–Alder reaction. Both methodologies behave similarly for all systems considered. In general, the SM-IQA diatomic xc components are less negative than the Hartree–Fock ones, which is in good agreement with the known effect of electron correlation upon (most) covalent bonds. In addition, a new general scheme to minimize the numerical error of the sum of two-electron energy contributions (i.e., Coulomb and exact exchange) in the framework of overlapping atoms is described in detail. [ABSTRACT FROM AUTHOR]

© 2015 Springer Science+Business Media Dordrecht Planted woodland islets act as sources of seed that may accelerate woodland development in extensive agricultural landscapes. We assessed a 1-ha plot that was planted with 16 100-m2 islets of holm oak Quercus ilex subsp. ballota seedlings near Toledo (Spain) in 1993. In spring 2014 we measured (1) acorn predation and (2) seedling emergence from seeded acorns at different distances from and orientations around the islets with half of the acorns protected to prevent predation, (3) survival of emerged seedlings, and (4) natural tree establishment outside of the planted islets. Most (96.9 %) unprotected acorns were removed or predated. Seedling emergence from protected acorns ranged from 42.9 % on the northern side of the islets to 13.2 % on the southern side, suggesting a less stressful microclimate on the northern side. Survival of naturally established seedlings was 28.6 % by the end of first summer; seedling mortality was chiefly due to drought (45.0 %) and herbivory (35.0 %). Density of emerged seedlings, surviving seedlings after first dry season, and established oaks >1-year old was similar at different distances from the islets. Over the 21 year time period, 58 new oak individuals >1-year old have established (an average of 3.3 established individuals per ha per year) at an average distance of 6.3 ± 5.4 m away from the closest islet. We conclude that initial oak regeneration triggered by small planted islets in Mediterranean abandoned farmland is slowed down by high acorn predation, seedling herbivory, and stressful microclimatic conditions. Regardless, these islets are a viable tool for regeneration of Mediterranean oak woodland.