Correction for 'Theoretical study on the mechanisms of formation of primal carbon clusters and nanoparticles in space' by Dobromir A. Kalchevski et al., Phys. Chem. Chem. Phys., 2024, https://doi.org/10.1039/d4cp02865a.

This work presents a comparative analysis of the results of silicon carbide synthesis through the carbonization of Si (001) and Si (111) substrates in the temperature range 1130–1140 °C. The synthesis involved chemical vapor deposition utilizing thermally stimulated methane reduction in a hydrogen gas stream. The experiments employed an Oxford Nanofab Plasmalab System 100 apparatus on substrates from which the native oxide was removed according to established protocols. To minimize random experimental variations (e.g., deviations from set parameters), short synthesis durations of 3 and 5 min were analyzed. The resultant thin films underwent evaluations through several techniques, including X-ray photoelectron spectroscopy, X-ray diffractometry, optical emission spectroscopy with glow discharge, and transmission electron microscopy. A comparison and analysis were conducted between the results from both substrate orientations.

We present a theoretical study of assembling clusters and nanoparticles in space from primordial aggregations of unbound carbon atoms. Geometry optimization and SCC-DFTB dynamics methods are employed to predict carbon clusters, their time evolution and stability. The initial density of the aggregates is found to be of primary importance for the structure of the clusters. Aggregates with low initial density yield clusters with an approximately equal prevalence of sp and sp2 hybridization with almost missing sp3. Higher initial density results in sp2-dominant molecules, resembling the carbon skeleton of polycyclic aromatic hydrocarbons (PAHs). Larger initial aggregations result in sp2-dominant polymers. Such materials are highly porous and possess a similarity to laterally bound nanotubes. Some clusters resemble fullerene building blocks. We employed metadynamics to model the inter-fragment coupling of such structures and predict the formation of spheroid nanoparticles, closely resembling fullerenes. One such structure has the lowest binding energy per atom among the studied molecules. All zero-dimensional forms, obtained by the simulations, conform to the experimentally detected types of molecules in space. The theoretical IR spectrum of the nanoparticles closely resembles that of fullerene C70 and therefore such imperfect structures may be mistaken for known fullerenes in experimental infrared (IR) telescope studies.

We present the results of silicon carbide (SiC) thin film synthesis on Si(111) substrates using chemical vapor deposition by decomposing CH4 in H2 at 1135 °C. The experiments were conducted in an Oxford Nanofab Plasmalab System 100 for carbon phase deposition times of 3, 5, 20, 60, and 90 min on Si(111) with or without native oxide, following established protocols. Our studies show that either predominantly crystalline SiC or a mixture of SiC and Si–O/Si–O–C glass forms on Si substrates significantly doped with carbon and oxygen, depending on the presence or absence of native oxide. The thickness of the SiC film ranges from approximately 5–6 nm for films synthesized in 3 min to over 15 nm for those synthesized in 90 min, while the size of the crystal grains varies from a few to 110 nm depending on the synthesis duration. The findings suggest that the complex composition of the thin films and the region beneath them can more effectively compensate for the differences in lattice parameters and thermal expansion coefficients between the SiC film and the Si substrate; thus, this method is promising for depositing intermediate thin films of SiC on Si substrates.

In this work, we present the results of measurements of the Raman spectrum of the root 3x root 3R30 degrees reconstruction of graphene grown on 4H-SiC(0001), the so-called buffer layer. The extracted Raman spectrum of the buffer layer shows bands, different from those of graphene, which can be attributed to the interaction of the buffer layer with the SiC substrate. In particular, in the high-wavenumber region, at least three bands are observed in the wavenumber regions 1,350-1,420, 1,470-1,490 and 1,520-1,570 cm-1. The assignment of the buffer layer bands is supported here by tight-binding simulations of the one-phonon density of states for structures with a sufficiently large number of Si-C bilayers for reaching convergence. The converged phonon density of states is found to be in semi-quantitative agreement with the latter two bands, and therefore, the tight-binding predictions of the lattice dynamics of the structure can be used for their assignment to buffer layer vibrations. Namely, the Raman band at about 1,550 cm-1 can be assigned to modified in-plane optical phonon branches of graphene, while the Raman band at about 1,490 cm-1 can be assigned to modified folded parts of these branches inside the Brillouin zone of the buffer layer and can be considered as a Raman fingerprint of the buffer layer. We present the results of measurements of the Raman spectrum of the root 3x root 3R30 degrees reconstruction of graphene grown on 4H-SiC(0001), the so-called buffer layer (BL) in the wavenumber region 1,200-1,650 cm-1. The assignment of the BL bands is supported by tight-binding simulations of the one-phonon density of states (DOS) for structures with a sufficiently large number of Si-C bilayers for reaching convergence. The converged phonon DOS is found to be in semi-quantitative agreement with the experimental Raman spectra.image

In this study, the CVD process of carbonization of {111} silicone surface is simulated employing ab initio metadynamics at the temperature of 1423 K. The entire chain of reactions is discovered, including the formation of an initial SiC crystallite seed with three carbon atoms, in the presence of native oxide. The characterization of all mechanisms includes transition states (TSs) and intermediate products. The forward free energy barriers were measured when possible. Carbonization always begins with alkylated surface products and progresses through loss of hydrogen. Only when all hydrogen atoms are lost, the carbon is accommodated in the crystal volume. Oxygen atoms of the native oxide may stay trapped in the SiC phase or in a buffer Si–C–O phase, forming a glass layer there. The native oxygen expresses certain mobility at the surface of the material. Occasionally TSs with hypervalent carbon and silicon atoms occur. The rate-determining reaction in the CVD synthesis of SiC has a free energy barrier of 173 kJ/mol.

The potential of semiconducting, corrugated graphene, grown on silicon carbide, as an active element in chemosensors is studied in the present work. For this purpose, the adsorption of benzene, diazepam and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) on the material’s surface was modeled. According to the graphene sheet bending and adsorbate–adsorbent distances, the heterostructure favors the ligands in the order of diazepam < benzene < TCDD. The apparent ambiguity in the results for diazepam is easy to explain. The abundance of lone pairs and π-electrons compensates for the low-symmetry, non-planar, far from optimal (adsorption-wise) geometry. The maximum band gap change in the heterostructure, caused by adsorption, is 0.02 eV. Intermolecular binding does not alter the HOMO–LUMO difference in benzene and TCDD by more than 0.01 eV. The completely planar molecules are not expected to undergo significant geometrical changes; hence, the alteration in their frontier orbitals is also minimal. The adsorption of diazepam, however, causes significant changes in the projected density of states of both structures in the complex. In conclusion, corrugated graphene is applicable as an active material in selective chemosensors for non-planar aromatic molecules.

In this study, the CVD process of carbonization of {111} silicone surface is simulated employing ab initio metadynamics at the temperature of 1423 K. The entire chain of reactions is discovered, including the formation of an initial SiC crystallite seed with three carbon atoms, in the presence of native oxide. The characterization of all mechanisms includes transition states (TSs) and intermediate products. The forward free energy barriers were measured when possible. Carbonization always begins with alkylated surface products and progresses through loss of hydrogen. Only when all hydrogen atoms are lost, the carbon is accommodated in the crystal volume. Oxygen atoms of the native oxide may stay trapped in the SiC phase or in a buffer Si–C–O phase, forming a glass layer there. The native oxygen expresses certain mobility at the surface of the material. Occasionally TSs with hypervalent carbon and silicon atoms occur. The rate-determining reaction in the CVD synthesis of SiC has a free energy barrier of 173 kJ/mol.

In this study, the CVD process of carbonization of {111} silicone surface is simulated employing ab initio metadynamics at the temperature of 1423 K. The entire chain of reactions is discovered, including the formation of an initial SiC crystallite seed with three carbon atoms, in the presence of native oxide. The characterization of all mechanisms includes transition states (TSs) and intermediate products. The forward free energy barriers were measured when possible. Carbonization always begins with alkylated surface products and progresses through loss of hydrogen. Only when all hydrogen atoms are lost, the carbon is accommodated in the crystal volume. Oxygen atoms of the native oxide may stay trapped in the SiC phase or in a buffer Si - C - O phase, forming a glass layer there. The native oxygen expresses certain mobility at the surface of the material. Occasionally TSs with hypervalent carbon and silicon atoms occur. The rate-determining reaction in the CVD synthesis of SiC has a free energy barrier of 173 kJ/mol.

Raman spectroscopy is one of the most suitable tools for studying few-layer graphene. The position of the G band and the defect-induced D and D' bands in the spectra of perfect single-layer graphene with sp 2 -hybridized carbon atoms and hydrogenated graphene with 27.7% sp 3 -hybridized carbon atoms are simulated using the Density Functional Theory (DFT) method with Perdew-Burke-Ernzerhof (PBE) functional. In the case of perfect graphene, the Raman G band is predicted at 1612 cm -1 . In the case of the hydrogenated structure, a new feature appears. Namely, along with the G band, now shifted to 1591 cm -1 , an additional feature, located at 1703 cm -1 , is clearly seen. The latter is due to oscillations, involving six atomic benzene rings, containing two sp 3 -hybridized C atoms. According to our results, the presence of defects, related to sp 3 hybridized carbon, gives rise to the appearance of the defect D' band in the Raman spectrum of defective graphene. This study shows that it is possible to simulate Raman spectra using the DFT method, with the results qualitatively matching the experimental data.

It has recently been shown both theoretically and experimentally that a significant modification of the aC:H films is possible using UV irradiation even with a very low irradiation fluence. Some initial results on the modification of aC:H films with thickness of about 40 nm with UV laser irradiation are presented here. The fourth harmonic (λ = 266 nm) of a Nd:YAG laser system (the fundamental wavelength λ = 1064 nm) was used in our experiments. The modified areas of the aC:H films were characterized by optical microscopy, Raman spectroscopy as well as by atomic force microscopy (AFM). A significant modification of aC:H films under certain conditions (laser irradiation fluence and modification modes) to multi-layer graphene accompanied by ablation of a part of the film was established. It was also found that similar aC:H films deposited on 330 nm SiO 2 /Si substrates did not undergo significant modification under these conditions.

The chemical interactions of two types of graphite and two types of carbon black (CB) with acetone, toluene, and phenol were studied in order to evaluate the influence of chemical treatment on the structure and morphology of the carbon phases. The experimental treatment of carbon phases was carried out at room temperature for 1 hour. The chemical and phase composition were studied by x-ray photoelectron (XP) and Raman spectroscopies, while the morphology and structure were determined by powder x-ray diffraction, as well as transmission electron microscopy techniques. To shed light on the most probable explanation of the observed results, we performed simulations and calculations of the binding energies of acetone, toluene, and phenol with model carbon phases: a perfect graphene sheet and a defective graphene sheet containing various structural defects (vacancies as well as zigzag and armchair edges). Simulations show that all non-covalent and most covalent coupling reactions are exothermic, with acetone coupling having the higher calorimetric effect. Based on the results of the simulations and the XP spectroscopy measurements, the probable reactions taking place during the respective treatments are outlined. The conducted studies (both theoretical and experimental) show that the treatment of graphite powders and CB with acetone, toluene, or phenol can be used as a preliminary stage of their modification and/or functionalization, including their conversion into graphene-like (defective graphene, reduced graphene oxide, and/or graphene oxide) phases. For example, the treatment of SPHERON 5000 with acetone significantly facilitates their subsequent modification with laser radiation to graphene-like phases.

A polymerization procedure is presented to increase the molecular weight of hydrocarbons in household chimney soot without thermal treatment at high temperatures. Pristine soot was subject to chlorination, with half of it treated with magnesium (Mg-plates) to create random-type Grignard reagents (R-Mg-Cl) in diethyl ether media. Mixing the Grignard reagent and the rest of the halogenated soot material created new C-C bonds, thus increasing the molecular weight of the final product. The obtained stochastically polymerized soot (SPS) was investigated using Raman spectroscopy, FTIR spectroscopy and XPS and was subjected to electrochemical testing as an assembled supercapacitor with a KOH electrolyte. Results show significant carbon structure differences due to the chemical procedures and newly created functional groups in the soot. Such functional groups could increase the capacity of supercapacitors, creating pseudo-capacitance by participating in redox reactions. The results also unveiled removing any random contaminations in the pristine soot and obtaining a more uniform final product containing hydrocarbons with longer chains, thus increasing the molecular weight.

The effect of modification of Cabot Corporation SPHERON 5000 carbon black suspended in bi-distilled water by laser irradiation (CuBr 2 laser with fundamental wavelength of λ = 511nm and 2 kHz repetition rate) has been studied. The carbon black suspensions were prepared by mixing 0.10 g carbon black previously treated with acetone in 100 ml bi-distilled water. Different laser beam fluencies and different irradiation times were used in order to optimize the modification process. The modified suspensions were decanted after sedimentation and dried. The powder fractions obtained were studied by scanning electron microscopy, X-ray diffraction and Raman spectroscopy.

Different nano-sized phases were synthesized using chemical vapor deposition (CVD) processes. The deposition took place on {001} Si substrates at about 1150–1160 °C. The carbon source was thermally decomposed acetone (CH3)2CO in a main gas flow of argon. We performed experiments at two ((CH3)2CO + Ar)/Ar) ratios and observed that two visually distinct types of layers were deposited after a one-hour deposition process. The first layer type, which appears more inhomogeneous, has areas of SiO2 (about 5% of the surface area substrates) beside shiny bright and rough paths, and its Raman spectrum corresponds to diamond-like carbon, was deposited at a (CH3)2CO+Ar)/Ar = 1/5 ratio. The second layer type, deposited at (CH3)2CO + Ar)/Ar = a 1/0 ratio, appears homogeneous and is very dark brown or black in color and its Raman spectrum pointed to defect-rich multilayered graphene. The performed structural studies reveal the presence of diamond and diamond polytypes and seldom SiC nanocrystals, as well as some non-continuously mixed SiC and graphene-like films. The performed molecular dynamics simulations show that there is no possibility of deposition of sp3-hybridized on sp2-hybridized carbon, but there are completely realistic possibilities of deposition of sp2- on sp2- and sp3- on sp3-hybridized carbon under different scenarios.

Here we present experimental results on the modification of graphite suspensions in bi-distilled water by laser irradiation in a flow mode system. The fundamental wavelength of a Nd:YAG laser system (λ= 1064 nm) was used in our experiments. The morphology of the sedimented and dried powders was studied by transmission electron microscopy (TEM). Their phase composition and structure were explored by Raman spectroscopy, GIXRD, as well as TEM.

In this paper electrical transport studies are performed on thin carbon films deposited on SiO 2 /Si substrates by pulsed laser deposition (PLD) applying laser ablation of micro-crystalline graphite target. Experiments were carried out on 320 - 420 nm thick SiO 2 on Si substrates as well as on hydrogenated diamond-like carbon (DLC) films deposited on SiO 2 /Si. Structural studies by means of XPS, SEM and Raman spectroscopy revealed that the films can be characterized as nano-sized carbon phases possessing different phase composition (i.e. the ratio sp 3 /sp 2 hybridized carbon, etc.). The electrical conductivity/resistivity of the films was measured in the temperature range 10 K < T < 300 K. Four-contact Van der Pauw method as well as two contact schemes have been applied. Some films have low room temperature resistivity in the range ρ = (0.1–1.5)×10 -3 Ω.·m and consist predominantly of sp 2 hybridized carbon with Raman spectra, which resemble that of nano-sized graphene depending on the deposition conditions and substrates used. The thinnest only 0.5 nm layer deposited directly on SiO 2 exhibits relatively low specific resistance (~10 -3 Ω. m), which can be taken as an indication of good deposition conditions of graphene-like layers. The current flow mechanism was explored at temperatures from 300 K down to 10K. The temperature dependence reveals non-metallic behavior - the conductivity decreases at decreasing temperature as opposed to typical metal behaviour. A model of variable range hopping (VRH) mechanism is applied to explain the low temperature conductivity drawn from transport in nanocrystalline disordered systems.

The present study investigates the possibility of obtaining graphene-like phases (defected graphene, graphene oxide, and reduced graphene oxide) as fine suspensions by applying a novel pulsed laser ablation (PLA) approach in flow mode. Two types of suspensions of microcrystalline graphite in aqueous suspensions and two types of microcrystalline graphite in suspensions of 6% hydrogen peroxide solution were irradiated in a quartz tube through which they flow. The third (λ = 355 nm) and fourth harmonics (λ = 266 nm) of an Nd:YAG laser system (15 ns pulse duration and 10 Hz pulse repetition rate) were used. The morphology of the obtained particles was studied by transmission electron microscopy (TEM). Their phase composition and structure were explored by X-ray photoelectron spectroscopy, X-ray diffractometry, and Raman spectroscopy.

The interactions between Na+ or Mg2+ ions with different parts of single-stranded RNA molecules, namely, the oxygen atoms from the phosphate groups or the guanine base, in water solution have been studied using first-principles molecular dynamics. Sodium ions were found to be much more mobile than Mg2+ ions and readily underwent transitions between a state directly bonded to RNA oxygen atoms and a completely solvated state. The inner solvation shell of Na+ ions fluctuated stochastically at a femtosecond timescale coordinating on average 5 oxygen atoms for bonded Na+ ions and 5.5 oxygen atoms for solvated Na+ ions. In contrast, the inner solvation shell of Mg2+ ions was stable in both RNA-bonded and completely solvated states. In both cases, Mg2+ ions coordinated 6 oxygen atoms from the inner solvation shell. Consistent with their stable solvation shells, Mg2+ ions were more effective than Na+ ions in stabilizing the RNA backbone conformation. The exclusion zones between the first and second solvation shells, solvation shell widths, and angles for binding to carbonyl oxygen of guanine for solvated Na+ or Mg2+ ions exhibited a number of quantitative differences when compared with RNA crystallographic data. The presented results support the distinct capacity of Mg2+ ions to support the RNA structure not only in the crystal phase but also in the dynamic water environment both on the side of the phosphate moiety and on the side of the nucleobase.