XDM-corrected hybrid DFT with numerical atomic orbitals predicts molecular crystal lattice energies with unprecedented accuracy

Molecular crystals are important for many applications, including energetic materials, organic semiconductors, and the development and commercialization of pharmaceuticals. The exchange-hole dipole moment (XDM) dispersion model has shown good performance in the calculation of relative and absolute lattice energies of molecular crystals, although it has traditionally been applied in combination with plane-wave/pseudopotential approaches. This has limited XDM to use with semilocal functional approximations, which suffer from delocalization error and poor quality conformational energies, and to systems with a few hundreds of atoms at most due to unfavorable scaling. In this work, we combine XDM with numerical atomic orbitals, which enable the efficient use of XDM-corrected hybrid functionals for molecular crystals. We test the new XDM-corrected functionals for their ability to predict the lattice energies of molecular crystals for the X23 set and 13 ice phases, the latter being a particularly stringent test. A composite approach using a XDM-corrected, 25% hybrid functional based on B86bPBE achieves a mean absolute error of 0.48 kcal mol⁻¹ per molecule for the X23 set and 0.19 kcal mol⁻¹ for the total lattice energies of the ice phases, compared to recent diffusion Monte-Carlo data. These results make the new XDM-corrected hybrids not only far more computationally efficient than previous XDM implementations, but also the most accurate density-functional methods for molecular crystal lattice energies to date.

A new implementation of the XDM dispersion model within FHI-aims allows efficient use of XDM-corrected hybrid functionals, found to be the most accurate DFT methods for molecular crystal lattice energies to date.     

Trichoderma Enzymes for Degradation of Aflatoxin B1 and Ochratoxin A

The contamination of agricultural products with mycotoxins causes risks to animal and human health and severe economic losses. Mycotoxicoses can be reduced by preventing fungal infection using chemical and biological approaches. The chemical strategies can release toxic molecules; therefore, strategies for biological control are being evaluated, such as using nontoxic fungi and their metabolites. This work evaluated the effect of exoenzymes produced by the beneficial fungus Trichoderma afroharzianum strain T22 in degrading Aflatoxin B1 (AFB1) and Ochratoxin A (OTA). The ability of Trichoderma to produce hydrolases was stimulated by using different inducing substrates. The highest AFB1 and OTA degradation activity was obtained using a medium containing lyophilized mushrooms and crude fiber. The T. afroharzianum T22’s ability to reduce mycotoxins may be attributed to peroxidase enzymes. This study showed that T. afroharzianum strain T22 or its peroxidase supplementation could represent a sustainable strategy for the degradation of AFB1 and OTA in feed and food products.     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

Resolving overlapping peaks in ARXPS data: The effect of noise and fitting method

Peak-fitting of X-ray photoelectron spectroscopy (XPS) data can be very sensitive to noise when the difference on the binding energy among the peaks is smaller than the width of the peaks. This sensitivity depends on the fitting algorithm. Angle-resolved XPS (ARXPS) analysis offers the opportunity of employing the combined information contained in the data at the various angles to reduce the sensitivity to noise. The assumption of shared peak parameters (center and width) among the spectra for the different angles, and how it is introduced into the analysis, plays a basic role. Sequential fitting is the usual practice in ARXPS data peak-fitting. It consist on first estimating the center and width of the peaks from the data acquired at one of the angles, and then using those parameters as a starting approximation for fitting the data for each of the rest of the angles. An improvement of this method consists of averaging the centers and widths of the peaks obtained at the different angles, and then employing these values to assess the areas of the peaks for each angle. Another strategy for using the combined information is by assessing the peak parameters from the sum of the experimental data. The complete use of the combined information contained in the data-set is optimized by the simultaneous fitting method. It consists of the assessment of the center and width of the peaks by fitting the data at all the angles simultaneously. Computer-generated data was employed to compare the sensitivity with respect to noise between the sequential, averaged-sequential, sum, and simultaneous fitting methods. It is shown that the latter is significantly more robust and could provide reliable results even for noisy data and small peak separation. The fundamentals for the robustness of the simultaneous method are discussed, as well as the possibility of fitting many parameters at the same time. As an added feature of ARXPS, it was found that the estimation of the error intervals on the peak parameters is done remarkably more precisely by employing XPS data at various angles.     

Radon Measure-Valued Solutions for a Class of Quasilinear Parabolic Equations

Initial value problems for quasilinear parabolic equations having Radon measures as initial data have been widely investigated, looking for solutions which for positive times take values in some function space. In contrast, it is the purpose of this paper to define and investigate solutions that for positive times take values in the space of the Radon measures of the initial data. We call such solutions measure-valued, in contrast to function-valued solutionspreviously considered in the literature. We first show that there is a natural notion of measure-valued solution of problem (P) below, in spite of its nonlinear character. A major consequence of our definition is that, if the space dimension is greater than one, the concentrated part of the solution with respect to the Newtonian capacity is constant in time. Subsequently, we prove that there exists exactly one solution of the problem, such that the diffuse part with respect to the Newtonian capacity of the singular part of the solution (with respect to the Lebesgue measure) is concentrated for almost every positive time on the set where “the regular part (with respect to the Lebesgue measure) is large”. Moreover, using a family of entropy inequalities we demonstrate that the singular part of the solution is nonincreasing in time. Finally, the regularity problem is addressed, as we give conditions (depending on the space dimension, the initial data and the rate of convergence at infinity of the nonlinearity ψ) to ensure that the measure-valued solution of problem (P) is, in fact, function-valued.     

The Reduction of Benzofuroxans by Ferrous Salts and by Thiophenol

Treatment of benzofuroxan derivatives with ferrous sulphate in DMSO/water solution affords in high yield o-nitroanilines. o-Nitroaniline was also obtained by reduction of benzofuroxan with thiophenol in presence of catalytic amount of Fe²⁺ or Fe³⁺ salts.     

Tailored pump-probe transient spectroscopy with time-dependent density-functional theory: controlling absorption spectra

Recent advances in laser technology allow us to follow electronic motion at its natural time-scale with ultra-fast time resolution, leading the way towards attosecond physics experiments of extreme precision. In this work, we assess the use of tailored pumps in order to enhance (or reduce) some given features of the probe absorption (for example, absorption in the visible range of otherwise transparent samples). This type of manipulation of the system response could be helpful for its full characterization, since it would allow us to visualize transitions that are dark when using unshaped pulses. In order to investigate these possibilities, we perform first a theoretical analysis of the non-equilibrium response function in this context, aided by one simple numerical model of the hydrogen atom. Then, we proceed to investigate the feasibility of using time-dependent density-functional theory as a means to implement, theoretically, this absorption-optimization idea, for more complex atoms or molecules. We conclude that the proposed idea could in principle be brought to the laboratory: tailored pump pulses can excite systems into light-absorbing states. However, we also highlight the severe numerical and theoretical difficulties posed by the problem: large-scale non-equilibrium quantum dynamics are cumbersome, even with TDDFT, and the shortcomings of state-of-the-art TDDFT functionals may still be serious for these out-of-equilibrium situations.