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Although the quality of weather forecasts in the polar regions is improving, forecast skill there still lags behind lower latitudes. So far there have been relatively few efforts to evaluate processes in numerical weather prediction systems using in situ and remote sensing datasets from meteorological observatories in the terrestrial Arctic and Antarctic compared to the mid-latitudes. Progress has been limited both by the heterogeneous nature of observatory and forecast data and by limited availability of the parameters needed to perform process-oriented evaluation in multi-model forecast archives. The Year of Polar Prediction (YOPP) site Model Inter-comparison Project (YOPPsiteMIP) is addressing this gap by producing merged observatory data files (MODFs) and merged model data files (MMDFs), bringing together observations and forecast data at polar meteorological observatories in a format designed to facilitate process-oriented evaluation. An evaluation of forecast performance was performed at seven Arctic sites, focussing on the first YOPP Special Observing Period in the Northern Hemisphere (NH-SOP1) in February and March 2018. It demonstrated that although the characteristics of forecast skill vary between the different sites and systems, an underestimation in boundary layer temperature variability across models, which goes hand in hand with an inability to capture cold extremes, is a common issue at several sites. It is found that many models tend to underestimate the sensitivity of the 2 m air temperature (T2m) and the surface skin temperature to variations in radiative forcing, and the reasons for this are discussed. [ABSTRACT FROM AUTHOR]

The rapid changes occurring in the polar regions require an improved understanding of the processes that are driving these changes. At the same time, increased human activities such as marine navigation, resource exploitation, aviation, commercial fishing, and tourism require reliable and relevant weather information. One of the primary goals of the World Meteorological Organization's Year of Polar Prediction (YOPP) project is to improve the accuracy of numerical weather prediction (NWP) at high latitudes. During YOPP, two Canadian "supersites" were commissioned and equipped with new ground-based instruments for enhanced meteorological and system process observations. Additional pre-existing supersites in Canada, the United States, Norway, Finland, and Russia also provided data from ongoing long-term observing programs. These supersites collected a wealth of observations that are well suited to address YOPP objectives. In order to increase data useability and station interoperability, novel Merged Observatory Data Files (MODFs) were created for the seven supersites over two Special Observing Periods (February to March 2018 and July to September 2018). All observations collected at the supersites were compiled into this standardized NetCDF MODF format, simplifying the process of conducting pan-Arctic NWP verification and process evaluation studies. This paper describes the seven Arctic YOPP supersites, their instrumentation, data collection and processing methods, the novel MODF format, and examples of the observations contained therein. MODFs comprise the observational contribution to the model intercomparison effort, termed YOPP site Model Intercomparison Project (YOPPsiteMIP). All YOPPsiteMIP MODFs are publicly accessible via the YOPP Data Portal (Whitehorse: 10.21343/a33e-j150, Huang et al., 2023a; Iqaluit: 10.21343/yrnf-ck57, Huang et al., 2023b; Sodankylä: 10.21343/m16p-pq17, O'Connor, 2023; Utqiaġvik: 10.21343/a2dx-nq55, Akish and Morris, 2023c; Tiksi: 10.21343/5bwn-w881, Akish and Morris, 2023b; Ny-Ålesund: 10.21343/y89m-6393, Holt, 2023; and Eureka: 10.21343/r85j-tc61, Akish and Morris, 2023a), which is hosted by MET Norway, with corresponding output from NWP models. [ABSTRACT FROM AUTHOR]

Although the quality of weather forecasts in the polar regions is improving, forecast skill there still lags the lower latitudes. So far there have been relatively few efforts to evaluate processes in Numerical Weather Prediction systems using in-situ and remote sensing datasets from meteorological observatories in the terrestrial Arctic and Antarctic, compared to the mid-latitudes. Progress has been limited both by the heterogeneous nature of observatory and forecast data but also by limited availability of the parameters needed to perform process-oriented evaluation in multi-model forecast archives. The YOPP site Model Inter-comparison Project (YOPPsiteMIP) is addressing this gap by producing Merged Observatory Data Files (MODFs) and Merged Model Data Files (MMDFs), bringing together observations and forecast data at polar meteorological observatories in a format designed to facilitate process-oriented evaluation. An evaluation of forecast performance was performed at seven Arctic sites, focussing on the first YOPP Special Observing Period in the Northern Hemisphere (SOP1), February and March 2018. It demonstrated that although the characteristics of forecast skill vary between the different sites and systems, an underestimation in boundary layer temperature variance across models, which goes hand in hand with an inability to capture cold extremes, is a common issue at several sites. Diagnostic analysis using surface fluxes suggests that this is at least partly related to insufficient thermal representation of the land-surface in the models, which all use a single layer snow model. [ABSTRACT FROM AUTHOR]

The adsorption of benzene, pyridine, and two nucleobases on the Au(111) surface has been investigated using a fully relaxed, self-consistent meta-generalized gradient approximation (meta-GGA) density functional theory setup with the M06-L functional. The meta-GGA based molecule-surface separations are shortened and the adsorption bond strengths of the molecules are greatly improved over the virtually non-interacting results obtained when using a plain GGA exchange-correlation functional. The nucleobases containing oxygen atoms show higher corrugation with adsorption site and orientation than the other aromatic molecules considered. The adsorption of pentacene is studied on Au, Ag, and Cu surfaces. In agreement with experiment, the adsorption energies are found to increase with decreasing nobleness, but the dependency is underestimated. We point out how the kinetic energy density can discriminate between covalent and non-covalent bonding regions of orbital overlap. [ABSTRACT FROM AUTHOR]

The theory and an implementation of the solvent contribution to the cubic response function for the polarizable continuum model for multiconfigurational self-consistent field wave functions is presented. The excited-state polarizability of benzene, para-nitroaniline, and nitrobenzene has been obtained from the double residue of the cubic response function calculated in the presence of an acetonitrile and dioxane solvent. The calculated excited-state polarizabilities are compared to results obtained from the linear response function of the explicitly optimized excited states. [ABSTRACT FROM AUTHOR]

The two-photon absorption of a class of [2.2]paracyclophane derivatives has been studied using quadratic response and density functional theories. For the molecules investigated, several effects influencing the two-photon absorption spectra have been investigated, such as side-chain elongation, hydrogen bonding, the use of ionic species, and solvent effects, the latter described by the polarizable continuum model. The calculations have been carried out using a recent parallel implementation of the polarizable continuum model in the DALTON code. Special attention is given to those aspects that could explain the large solvent effect on the two-photon absorption cross sections observed experimentally for this class of compounds. [ABSTRACT FROM AUTHOR]

Solvent effects on the two-photon absorption of a symmetrical diamino substituted distyrylbenzene chromophore have been studied using the density functional response theory in combination with the polarizable continuum model. It is shown that the dielectric medium has a rather small effect both on the bond length alternation and on the one-photon absorption spectrum, but it affects significantly the two-photon absorption cross section. It is found that both one- and two-photon absorptions are extremely sensitive to the planarity of the molecule, and the absorption intensity can be dramatically reduced by the conformation distortion. It has led to the conclusion that the experimentally observed anomalous solvent effect on the two-photon absorption of dialkylamino substituted distyrylbenzene chromophores cannot be attributed to the intrinsic properties of a single molecule and its interaction with solvents. [ABSTRACT FROM AUTHOR]

We present a parallel implementation of the integral equation formalism of the polarizable continuum model for Hartree-Fock and density functional theory calculations of energies and linear, quadratic, and cubic response functions. The contributions to the free energy of the solute due to the polarizable continuum have been implemented using a master-slave approach with load balancing to ensure good scalability also on parallel machines with a slow interconnect. We demonstrate the good scaling behavior of the code through calculations of Hartree-Fock energies and linear, quadratic, and cubic response function for a modest-sized sample molecule. We also explore the behavior of the parallelization of the integral equation formulation of the polarizable continuum model code when used in conjunction with a recent scheme for the storage of two-electron integrals in the memory of the different slaves in order to achieve superlinear scaling in the parallel calculations. [ABSTRACT FROM AUTHOR]

We present an implementation of the polarizable continuum model in its integral equation formulation for the calculation of the magnetizabilities of solvated molecules. The gauge-origin independence of the calculated magnetizabilities and the fast basis set convergence are ensured through the use of London atomic orbitals. Our implementation can use Hartree-Fock and multiconfigurational self-consistent-field (MCSCF) wave functions as well as density-functional theory including hybrid functionals such as B3LYP. We present the results of dielectric continuum effects on water and pyridine using MCSCF wave functions, as well as dielectric medium effects on the magnetizability of the aromatic amino acids as a model for how a surrounding protein environment affects the magnetizability of these molecules. It is demonstrated that the dielectric medium effects on the magnetizability anisotropies of the aromatic amino acids may be substantial, being as large as 25% in the case of tyrosine. [ABSTRACT FROM AUTHOR]

We present the first implementation of the quadratic response function for multiconfigurational self-consistent-field wave functions of solvated molecules described by a polarizable continuum model employing a molecule-shaped cavity. We apply the methodology to the first hyperpolarizability β and, in particular, the second-harmonic generation process for a series of conjugated push-pull oligomers, as well as for para-nitroaniline. The effect of solvation on the dispersion of the hyperpolarizability and the change in the hyperpolarizability for increasing chain length of the oligomers in vacuum and in solution is considered. The effect of a correlated description is analyzed by comparing the Hartree-Fock hyperpolarizabilities to the multiconfigurational self-consistent-field hyperpolarizabilities. The effect of geometry relaxation in the solvent on the properties of the solvated molecules are also investigated. [ABSTRACT FROM AUTHOR]

The application of the recently developed second-order n-electron valence state perturbation theory (NEVPT2) to small carbonyl molecules (formaldehyde, acetaldehyde, and acetone) is presented. The adiabatic transition energies are computed for the singlet and triplet n→π*, π→π*, and σ→π* states performing a full geometry optimization of the relevant states at the single state CASSCF level and taking into account the zero point energy correction in the harmonic approximation. The agreement with the known experimental values and with previously published high level calculations confirms that NEVPT2 is an efficient tool to be used for the interpretation of molecular electronic spectra. Moreover, different insight into the nature of the excited states has been obtained. Some of the transitions presented here have never been theoretically computed previously [3(π→π*) and 3(σ→π*) adiabatic transitions in acetaldehyde and acetone] or have been studied only using moderate level (single reference based) ab initio methods (all adiabatic transitions in acetaldehyde). In the present work a consistent disagreement between NEVPT2 and experiment has been found for the 3(π→π*) adiabatic transition in all molecules: this result is attributed to the low intensity of the transition to the first vibrational levels of the excited state. The n→π* singlet and triplet vertical transition energies are also reported for all the molecules. [ABSTRACT FROM AUTHOR]

A density functional theory study of the energetics of isolated [Au.sub.n.sup.+] (n = 5-10) and [Au.sub.n.sup.-] (n = 8?13) gold clusters are presented. The stronger tendency exhibited by the meta-generalized gradient approximation (MGGA) toward 3D structures are found to originate from their smaller gradient enhancement.

The second-order nonlinear optical properties of green fluorescent proteins (GFPs) like the photoswitchable Dronpa and enhanced GFP (EGFP) are studied. The second-order nonlinear optical properties of GFP-like proteins are important for the combined nonlinear microscopy based on existing fusion proteins involving GFPs.

Density functional theory (DFT) cubic response theory and the polarizable continuum model are used for studying the solvent-induced three-photon absorption cross section of a highly conjugated fluorene derivative. It is shown that the simplified model performs poorly for the three-photon absorption properties of the symmetric charge-transfer molecule and the dielectric medium has increased the three-photon absorption cross section.

The theory and implementation of the solvent contribution to the cubic response function of a molecular solute for the polarizable continuum model in its integral equation formulation which could be used to compute the solvent effect for the degenerate four-wave mixing process for different classes of heteroaromatic chromophores are described.