A comprehensive theoretical study of selected point defects for a monolayer of hexagonal boron nitride (h‐BN) is presented. Two‐dimensional structures were simulated through large h‐BN molecular clusters and used to examine various defects, like: atom vacancies, atom substitutions, or distortions of the hexagonal lattice. Since carbon contaminations are very common in the h‐BN technology, a particular attention has been paid to carbon impurities. The calculations of IR spectra for the doped molecular clusters reveal the presence of additional frequencies, which in many cases correspond to defect‐bound modes. In particular, when two carbon atoms are close to each other, a localized stretching CC mode of a high intensity has been found, with a frequency value of about 100‐200 cm–1 higher than for collective BN stretch frequencies. Absorption UV‐Vis spectra obtained from time‐dependent density functional theory show that the inclusion of impurities results in an emergence of several low‐energy electronic excitations, from which some are localized on a defect, while other are delocalized. Energies of these excitations are strongly dependent on the defect type, and they range from about 0.7 to 6.1 eV for the lowest excitations. Based on UV‐Vis spectra we propose several candidates which could be responsible for the experimental 4 eV color band. These defects are built from two or four adjacent carbon atoms and have the lowest excitation ranging from 3.9 to 4.8 eV, which is strongly localized on the defect.

A dimerization of methyl chlorophyllide a molecules and a role of water in stabilization and properties of methyl chlorophyllide a dimers were studied by means of symmetry-adapted perturbation theory (SAPT), functional-group SAPT (F-SAPT), density-functional theory (DFT), and time-dependent DFT approaches. The quantification of various types of interactions, such as π–π stacking, coordinative, and hydrogen bonding by applying the F-SAPT energy decomposition scheme shows the major role of the magnesium atom and the pheophytin macrocycle in the stability of the complex. The examination of interaction energy components with respect to a mutual orientation of monomers and in the presence or absence of water molecules reveals that the dispersion energy is the main binding factor of the interaction, while water molecules tend to weaken the attraction between methyl chlorophyllide a species. The dimerization can be seen in computed UV–vis spectra, and results in a doubling of the lowest peaks, as compared to the monomer spectrum, and in an intensity rise of the lowest 1.8 and 2.4 eV peaks at a cost of the 3.5 eV peaks for the majority of dimer configurations. The complexation of water has little effect on the peaks’ position; however, it affects the overall shape of simulated spectra through changes in peak intensities, which is strongly dependent on the structure of the complex. The VCD spectra for the dimers show several characteristic features attributed to the interaction of substituting groups and/or water ligand attached to macrocycle groups belonging to different monomers. VCD is sensitive to the type of the formed dimer, but not to the number of water molecules it contains. This and several other features, as well as the differential UV–vis spectra, may serve as the indicator of the presence of a given dimer structure in the experiment.

The interaction of 1,2-dihydro-1,2-, 1,3-dihydro-1,3- and 1,4-dihydro-1,4-azaborine isomers with one and two water molecules has been studied using a variety of supermolecular (Møller-Plesset = MP, and coupled cluster = CC) as well as perturbational (symmetry-adapted perturbation theory = SAPT) electron-correlation methods in the complete basis-set limit. It has been found that the water molecule binds to azaborine isomers through O-H···π, π-H···O, and dihydrogen bonding linkages. The SAPT interaction energy decomposition shows that these complexes are mostly stabilized by dispersion followed closely by induction contributions. Pauli repulsion hinders water molecule to be polarized by azaborine in the O-H···π type of complexes. According to the interacting-quantum-atoms analysis, the structures with a primary binding of the O-H···π type benefit from an additional stabilization factor resulting from the interaction of the oxygen and the second hydrogen atom of water, i.e., the one which does not point toward the ring, while the interaction of hydrogens from water with azaborines plays a destabilizing role for the π-H···O type. The same method states that the intermolecular bindings between azaborines and the water molecule have a multicenter character with a small bond polarization, and they are classified as closed-shell (noncovalent) by quantum theory of atoms-in-molecules analysis at bond critical points. The complexes of azaborines with two water molecules tend to arrange in a circular fashion with a recognizable water dimer attached to the azaborine molecule. A comparison with the CCSD(T) benchmarks shows that the nonadditive contribution to the interaction energy of the trimers is negative and with a good accuracy can be accounted for by the MP2 method. A good agreement between Hartree-Fock (HF) and MP2 nonadditive energy, as well as the decomposition of HF nonadditive interaction energies divulge the importance of nonadditive induction energy in the trimers. The interaction energies for the azaborine with one water calculated with the SAPT(DFT), MP2, SCS-MP2, and MP2C methods are in satisfactory agreement with each other. Finally, it has been found that the population analysis from the electron localization function offers the most comprehensive explanation of the orientational preferences of the water molecule in the complex.

The paper describes the first electrochemical method (differential pulse adsorptive stripping voltammetry, DPAdSV) using a screen‐printed sensor with a carbon/carbon nanofibers working electrode (SPCE/CNFs) for the direct determination of low (real) concentrations of paracetamol (PA) in environmental water samples. By applying this sensor together with DPAdSV, two linear PA concentration ranges from 2.0×10−9 to 5.0×10−8 mol L−1 (r=0.9991) and 1.0×10−7–2.0×10−6 mol L−1 ( r=0.9994) were obtained. For the accumulation time of 90 s, the limit of detection was 5.4×10−10 mol L−1. Moreover, the SPCE/CNFs sensor and the DPADSV procedure for PA determination are potentially applicable in field analysis. The process of PA adsorption at the SPCE/CNFs surface was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and theoretical studies. In the theoretical study of the interaction of CNF and PA, the first species was modelled by graphene‐like clusters containing up to 37 rings. It was found that the preferable orientation of PA is parallel to the carbon surface with the binding energy of about −68 kJ/mol calculated by symmetry‐adapted perturbation theory (SAPT). Both the selectivity and the accuracy of the developed sensor for real sample analysis were also investigated using Polish river and sea samples.

Influence of the additional layer of hexagonal boron nitride (h-BN) on structure, energetics, and electronic spectra of a layer doped with magnesium, silicon, phosphorus, aluminum, or carbon atoms has been examined by theoretical methods. The h-BN layers are modeled as BN clusters of over thirty atoms with the defect in the center. The calculations show that atom positions undergo some modifications in the presence of the second layer, which in several cases lead to significant changes in electronic spectra, like (i) modifications of the character of some states from local excitation to a partial charge transfer; (ii) redshift of the majority of lowest excitations; (iii) absence or appearance of new states in comparison with the monolayers. For instance, a zero-intensity excitation below 4 eV for the carbon atom in place of boron transforms into a dipole-allowed one in the presence of the second layer. A comparison of the interaction energies of doped and undoped clusters shows a strong dependence of the stabilizing of destabilizing effect on the dopant atom, the replaced atom, and in some cases also on the stacking type (AA’ or AB). The stabilization energy per BN pair, calculated for two undoped clusters, is equal to − 31 and − 28 meV for the AA’ and AB stacking, respectively, thus confirming a larger stability of the AA’ stacking for the h-BN case. Electronic supplementary material The online version of this article (10.1007/s00894-020-04456-8) contains supplementary material, which is available to authorized users.