Towards understanding the first half-ALD cycle of Ag growth: adsorption and dissociation of silver(I) acetamidinates on the Ag(110) surface.

The advancement of atomic layer deposition (ALD) techniques for the controlled growth of transition metal thin films is constantly growing due to the design and synthesis of novel organometallic (OM) precursors capable of facilitating precise deposition and clean film growth. In this context, acetamidinates have emerged as a highly promising family of OM precursors due to their exceptional attributes, including outstanding stability, favorable volatility, and reactivity at low evaporation and deposition temperatures. These unique properties make them a sought-after candidate for enabling ALD processes. Here we conducted an atomic-scale study to get an in-depth understanding of the first ALD partial reaction, which involves the adsorption and dissociation process of the silver acetamidinate on the Ag(110) surface. Our research sheds light on the multistep adsorption and breaking mechanism of the novel silver(I)-N,N'-dimethylacetamidinate precursor employed as the silver source. Since the difference in energy between the monomer and dimer phases of the precursor is only 1.92 eV, we have explored the adsorption states of both phases. The monomer adsorbs on the surface by occupying hollow (H) sites; after that, it dissociates and loses its ligand, adopting a perpendicular geometry via the formation of new Ag-N bonds with the pair of N atoms at the top sites of the surface. On the other hand, the dimer adsorbs on long-bridge sites (LB) with the pair of N atoms occupying top sites with the silver atoms from the surface. Next, the dimer loses a pair of N-Ag bonds on each ligand, reaching a more stable state of partial cleavage with a relative energy of -0.38 eV. After overcoming an energy barrier of 0.41 eV, the dimer loses the remaining pair of N-Ag bonds, and the silver atoms diffuse towards H sites. Finally, the ligands diffuse toward the adjacent channel in the [100] direction of the surface. A charge distribution analysis of the adsorption stages shows the evolution of the silver atoms from precursor to the metallic state.

Reliability and validity of the Japanese version of the Ullanlinna Narcolepsy Scale and Swiss Narcolepsy Scale for screening Japanese individuals with narcolepsy type 1.

OBJECTIVE: To validate the Japanese versions of the Ullanlinna Narcolepsy Scale (J-UNS) and Swiss Narcolepsy Scale (J-SNS) for screening narcolepsy in the Japanese population and to discuss strategies for their use in hypersomniac individuals. METHODS: We selected 451 outpatients with excessive daytime sleepiness (EDS) already diagnosed according to the International Classification of Sleep Disorders third edition. They responded to both scales twice at 1-month intervals. After eliminating individuals who met the exclusion criteria, validity and reliability analyses were performed on 408 and 381 participants, respectively. RESULTS: Patients with narcolepsy type 1 (NT1) displayed higher J-UNS and lower J-SNS scores than those with NT2 and other sleep disorders. The intraclass correlation coefficients and weighted κ coefficient for scale scores in the total participants and patients with NT1 were ≥0.70 and ≥ 0.40, respectively, indicating high reliability. Furthermore, both the sensitivity and specificity of these scales upon using the original cut-off scores (14 for UNS and 0 for SNS) for detecting NT1 were 0.70 or ≥0.70, suggesting high validity. Additionally, the receiver operating characteristic curve analysis revealed that the best cut-off score did not change for the J-SNS but that for the J-UNS, it increased to 18. In our study, the scale's sensitivity and specificity changed from 96% to 82% and 58%-78%, respectively. CONCLUSIONS: Both scales revealed satisfactory screening abilities for NT1 in the Japanese population. However, it may be better to use J-UNS cut-off scores of 18 for a population with EDS.

Electronic and optical properties of the buckled and puckered phases of phosphorene and arsenene.

Using first-principles calculations, we have investigated the structural, electronic, and optical properties of phosphorene and arsenene, group V two-dimensional materials. They have attracted the scientific community's interest due to their possible applications in electronics and optoelectronics. Since phosphorene and arsenene are not planar monolayers, two types of structures were considered for each system: puckered and buckled arrangements. Computations of band gap were performed within the GW approach to overcome the underestimation given by standard DFT and predict trustable band gap values in good agreement with experimental measurements. Our calculated electronic band gaps lie in the range from near-infrared to visible light, suggesting potential applications in optoelectronics devices. The computed electronic band gaps are 2.95 eV and 1.83 eV for blue and black phosphorene systems. On the other hand, the values for buckled and puckered arsenene are 2.56 eV and 1.51 eV, respectively. Moreover, the study of the optical properties has been dealt by computing the dielectric function imaginary part, which was obtained using the Bethe-Salpeter approach. The use of this technique allows the consideration of excitonic effects. Results indicate strong exciton binding energies of 830 meV for blue phosphorene, 540 meV for black phosphorene, 690 meV for buckled arsenene, and 484 meV for puckered arsenene. The results of our study suggest the possibility of using these materials in electronic and optoelectronic devices.

Atomic-scale understanding of the Na and Cl trapping on the Mo1.33C(OH)2-MXene.

Drinking water scarcity in arid and semi-arid regions is a reality that may turn into a global healthcare problem in the next few years. The scientific community is always looking for new materials to achieve effective sea and brackish water desalination to reduce water scarcity. Commonly, theoretical, and experimental methods make a synergy to better understand and explain the chemical and physical processes in water desalination electrodes. In this way, experimental evidence pointed Mo1.33CTx MXene as an efficient ion intercalation material, in which both Na+ and Cl- are removed. However, the atomic scale understanding of the physicochemical processes due to the Na and Cl interaction with the MXene is still unknown. We report the Na0 and Cl0 interaction with an OH functionalized Mo1.33C monolayer through a comprehensive first-principles density functional theory assessment. Results demonstrate that Na atoms attach to Oxygen, whereas Cl atoms bond through hydrogen bonds to the functional groups in the MXene, these bonds have two energy contributions: electrostatic and charge transfer, which increases its adsorption energy. Electrostatic potential isosurfaces, Bader charge analysis, and non-covalent interactions index help clarifying the way Na0 and Cl0 attach to the MXene layer. Oxygen atoms have an affinity for the electropositive Na0 atoms, which after interaction oxidizes to Na+, whereas hydrogen atoms-of the hydroxyl groups-interact with the electronegative Cl0 atoms, which upon adsorption reduce to Cl-. Our findings explain why OH-functionalized Mo1.33C can efficiently remove both Na and Cl atoms based on their affinities with the functional groups present in the MXene layer.

Metabolic-Syndrome-Related Comorbidities in Narcolepsy Spectrum Disorders: A Preliminary Cross-Sectional Study in Japan.

Narcolepsy types 1 (NT1) and 2 (NT2) and idiopathic hypersomnia (IH) are thought to be a disease continuum known as narcolepsy spectrum disorders (NSDs). This study aimed to assess the prevalence of and factors associated with metabolic-syndrome-related disorders (MRDs) among patients with NSD. Japanese patients with NSD (NT1, n = 94; NT2, n = 83; and IH, n = 57) aged ≥35 years were enrolled in this cross-sectional study. MRD was defined as having at least one of the following conditions: hypertension, diabetes, or dyslipidemia. Demographic variables and MRD incidence were compared among patients in the respective NSD categories. Multivariate logistic regression analysis was used to investigate the factors associated with MRDs. Patients with NT1 had a higher body mass index (BMI) and incidence of MRD than that had by those with NT2 or IH. Age, BMI, and the presence of OSA were significantly associated with the incidence of MRD in NSDs. Age and BMI in NT1, BMI and human leukocyte antigen (HLA)-DQB1*06:02 positivity in NT2, and only age in IH were factors associated with the incidence of MRD. Obesity should be carefully monitored in narcolepsy; however, NT2 with HLA-DQB1*06:02 positive should be followed up for the development of MRD even without obesity.

Adsorption of crotonaldehyde on metal surfaces: Cu vs Pt.

The thermal chemistry of crotonaldehyde on the surface of a polished polycrystalline copper disk was characterized by temperature-programmed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS) and contrasted with previous data obtained on a Pt(111) single crystal substrate. A clear difference in the adsorption mode was identified between the two surfaces, highlighted by the prevalence of RAIRS peaks for the C=C bond on Cu vs for C=O on Pt. Adsorption was also determined to be much weaker on Cu vs Pt, with an adsorption energy on the former ranging from -50 kJ/mol to -65 kJ/mol depending on the surface coverage. The experimental data were complemented by extensive quantum mechanics calculations using density functional theory (DFT) to determine the most stable adsorption configurations on both metals. It was established that crotonaldehyde adsorption on Cu occurs via the oxygen atom in the carbonyl group, in a mono-coordinated fashion, whereas on Pt multi-coordination is preferred, centered around the C=C bond. The contrasting surface adsorption modes seen on these two metals are discussed in terms of the possible relevance to selectivity in single-atom alloy hydrogenation catalysis.

A first-principles study of the atomic layer deposition of ZnO on carboxyl functionalized carbon nanotubes: the role of water molecules.

The formation of heterostructures that combine a large surface area with high surface activity has attracted the attention of the scientific community due to the unique properties and applications of these heterostructures. In this work, we describe - at the atomic level - the full reaction mechanisms involved in the atomic layer deposition of a hybrid ZnO/CNT inorganic structure. First, the pristine CNTs are chemically activated with a carboxylic acid, a process unique to carbon materials. Diethylzinc (DEZ) and water are used as gas-phase precursors to form ZnO. Our findings show that DEZ is physically adsorbed on the CNTs during the exposure of the first precursor. The ligand-exchange to generate chemisorbed ethyl zinc on the O side of the COOH group needs to overcome an energy barrier of 0.06 eV. This is a very small energy if compared to the values (0.5-0.6 eV) obtained in previous studies for OH functionalized surfaces. The height of the barrier is associated with the C[double bond, length as m-dash]O side, which mediates the H proton's exchange from the OH group to the C2H5 ligand. Furthermore, upon exposure to the oxidizing agent (H2O), ethyl zinc exchanges its last ligand as ethane, and it accepts a hydroxyl group through a self-limiting reaction with an energy barrier of 0.88 eV. Notice that the energy barrier of the second ligand-exchange is larger than of the first. We have also analyzed the effect in the saturation of the second precursor: as the quantity of water molecules increases, the long-range interactions tend to repel them. However, the energy barrier of the second ligand-exchange decreases from 1.53 eV to 0.88 eV for one and two water molecules, showing a clear dependence on the oxidizing agent. Non-covalent interactions are used as a tool to visualize the driving forces that take place during each partial reaction in real space. Our study points out the importance of using the right functionalization agent to achieve a controlled and conformal ALD growth at the initial steps of the formation of hybrid ZnO/CNT structures, as well as the role played by the oxidizing agent to lower the energy barrier on the second ALD step.

First-principles studies of the strain-induced band-gap tuning in black phosphorene.

Using first-principles calculations, we have studied the band-gap modulation as function of applied strain in black phosphorene (BP). Dynamical stability has been assessed as well. Three cases have been considered, in the first and second, the strain was applied uniaxially, in thex- andy-axis, separately. In the third, an isotropic in-plane strain was analyzed. Different strain percentages have been considered, ranging from 4% to 20%. The evolution of the band-gap is studied by using standard DFT and the G0W0approach. The band-gap increases for small strains but then decreases for higher strains. A change in electronic behavior also takes place: the strained systems change from direct to indirect band-gap semiconductor, which is explained in terms of thesandp-orbitals overlap. Our study shows that BP is a system with a broad range of applications: in band-gap engineering, or as part of van der Waals heterostructures with materials of larger lattice parameters. Its stability, and direct band-gap behavior are not affected for less than 16% of uniaxial and biaxial strain. Our findings show that phosphorene could be deposited in a large number of substrates without losing its semiconductor behavior.

Structural properties and thermal stability of multi-walled black phosphorene nanotubes and their operation as temperature driven nanorotors.

In this paper, we explore the influence of structural properties, thermal stability, and temperature on the rotational frequency of (0,n) armchair multi-walled black phosphorene nanotubes (MWßPNTs). Using Density Functional Theory (DFT) calculations, we first determine the influence of the outer wall rotation on the structural stability of (0,12)@(0,19) DWßPNTs, and (0,12)@(0,19)@(0,26) TWßPNTs. The results indicate that the relative energies of the DW- and the TWßPNTs do not change with the rotation angle. Therefore, the outer wall rotation is not important for the structural formation of the MWßPNTs. Then, using molecular dynamics (MD) simulations, we study the structural properties, thermal stability, and rotational frequency of (0,12)@(0,19) DWßPNTs, (0,12)@(0,19)@(0,26) TWßPNTs, and (0,12)@(0,19)@(0,26)@(0,33) QWßPNTs from 1 K to 400 K. The calorific curve, the mean-squared displacement, and the radial distribution function are analyzed to characterize the temperature behavior of the MWßPNTs. In all cases, the nanotubes are rotating: they act as thermal-driven rotors as the temperature increases, with a maximum rotational frequency of 16.7 GHz (clockwise direction) at 5 K for the DWßPNTs. Our results suggest that MWßPNTs could be used to construct room temperature nanomotors.

Understanding the first half-ALD cycle of the ZnO growth on hydroxyl functionalized carbon nanotubes.

We report the adsorption of diethylzinc on hydroxyl functionalized carbon nanotubes. This study intends to understand, at the atomic level, the initial stages of ZnO formation by atomic layer deposition. Our study begins with the molecule physisorbed on the nanotube (initial state of the reaction). The final state of this reaction is when the H atom of the hydroxyl group is abstracted and migrates to one ethyl group of diethylzinc. The oxygen atom relaxes towards the nanotube and forms a strong bond with a carbon atom, while the remaining part of the molecule forms a bond with the H atom and physisorbs on top of the ZnO unit. The probability for this process to happen is very high since the energy to desorb the diethylzinc molecule is higher than the energy needed to break down the O-H bond. Non-covalent interactions and charge density distributions are plotted to confirm the break-down, formation of bonds, and repulsion during the reaction pathway.

Prevalence and clinical characteristics of REM sleep behavior disorder in Japanese elderly people.

STUDY OBJECTIVES: To evaluate the prevalence and clinical characteristics of isolated REM sleep behavior disorder (iRBD) among a general population of elderly Japanese people. METHODS: This epidemiological study targeted 2714 elderly residents (76.0 ± 8.0 years, 52.9% female) of a rural community. Questionnaires including the REM sleep behavior disorder single question and demographic information were distributed. All respondents with the question positive were interviewed by telephone. Respondents suspected of having iRBD proceeded to face-to-face interviews and underwent video-polysomnography and neurological/neuropsychological examination. These results were compared to those of previously diagnosed clinical iRBD patients in our sleep clinic. RESULTS: Of 1464 respondents to the questionnaire, 18 respondents were diagnosed as iRBD (1.23 [0.66-1.79]%), including eight respondents who satisfied diagnostic criteria with REM sleep without atonia (RWA) above the cut-off value (0.54 [0.17-0.92]%) and 10 respondents who had clear dream enactment behaviors but not RWA above the cut-off (provisionally diagnosed iRBD; p-iRBD) (0.69 [0.26-1.11]%). Severity of RBD and RWA of the population-based iRBD were compatible with those of the clinical iRBD. Half of the population-based iRBD showed orthostatic hypotension and they showed lower olfactory function than population-based p-iRBD and non-RBD. However, their olfactory and cognitive functions were higher than those in the clinical iRBD patients. CONCLUSIONS: Prevalence of iRBD in Japanese elderly people was comparable with the rate reported from other countries. Population-based iRBD/p-iRBD showed lower neurodegenerative loading than clinical iRBD in spite of comparable disease duration of RBD, that may indicate their lower risk of future neurodegeneration.

Gender differences in clinical findings and α-synucleiopathy-related markers in patients with idiopathic REM sleep behavior disorder.

BACKGROUND: Rapid eye movement (REM) sleep behavior disorder (RBD) is a male-predominant parasomnia. Earlier clinical RBD patient studies showed gender differences of clinical symptoms and polysomnographic (PSG) findings. However, no previous investigated this issue by means of validated severity scales or by neuropsychological examination related to alpha-synucleinopathy. This study elucidates gender differences in clinical, physiological, and neuropsychological findings in Japanese idiopathic RBD (iRBD) patients. METHODS: From 220 patients with complaint of sleep-related vocalization or behaviors who visited Yoyogi Sleep Disorder Center from June 2003 through December 2016, 43 female (68.7 ± 7.3 yr) and 141 male patients (66.7 ± 6.7 yr) diagnosed as having iRBD by video-polysomnography (v-PSG) were selected. All subjects answered the RBD questionnaire (RBDQ-JP) and underwent olfactory function test (Sniffin' Sticks test) and cognitive function test (MoCA-J). RESULTS: Female iRBD patients had later first symptom-witnessed age (sleep-talking 63.2 ± 10.5 yr, behaviors 60.9 ± 8.6 yr) than male patients (sleep-talking 59.1 ± 8.8 yr, behaviors 64.7 ± 8.9 yr). No gender difference was found in age at diagnosis, clinical severity (RBDQ-JP), or olfactory or cognitive function. Regarding electromyogram (EMG) findings during REM sleep, phasic EMG activity was higher in female patients (22.3 ± 17.8% vs. 16.5 ± 16.1%), although no difference was found in tonic EMG activity. CONCLUSIONS: Although female iRBD patient symptoms were first recognized later than those of male patients, they showed elevated EMG activity during REM sleep and showed deteriorated olfactory and cognitive function similarly to male patients at the first medical consultation. Results suggest that disease progression in female RBD patients is equivalent to that in male patients.

Determining Surface Terminations and Chirality of Noncentrosymmetric FeGe Thin Films via Scanning Tunneling Microscopy.

Scanning tunneling microscopy was used to study the surfaces of 20-100 nm thick FeGe films grown by molecular beam epitaxy. An average surface lattice constant of ∼6.8 Å, in agreement with the bulk value, was observed via scanning tunneling microscopy, low energy electron diffraction, and reflection high energy electron diffraction. Each of the four possible chemical terminations in the FeGe films were identified by comparing atomic-resolution images, showing distinct contrast with simulations from density functional theory calculations. A detailed study of the atomic layering order and registry across step edges allows us to uniquely determine the grain orientation and chirality in these noncentrosymmetric films.

Structural transition induced by compression and stretching of puckered arsenene nanotubes.

The stretching and compression effects on puckered arsenene nanotubes (AsNTs) are investigated by using density functional calculations. The atomic arrangement determines the nanotube properties and relative stability; therefore, zigzag, chiral, and armchair present different properties. Since the AsNT properties depend on the diameter, three cases are considered: (a) (0, 9) and (9, 0), (b) (0, 14) and (14, 0), and (c) (0, 19) and (19, 0) NTs. For all calculated parameters of the smallest NTs, it is found that the armchair (0, 9) nanotube is always more stable than the zigzag (9, 0) nanotube. On the other hand, for the two largest NTs, a structural transition from armchair to zigzag is found upon stretching. Phase transitions are of great interest, in part because they result in changes of the properties of the material under study, changes that can be used in many technologies. To our knowledge, this is the first time that a structural transition in a puckered nanotube has been predicted. Our results show that the electronic band gap of the AsNTs can be modulated by increasing or decreasing the axial lattice parameter. It is also found that semiconductor NTs are more stable than metallic NTs.

Functionalization of silicene and silicane with benzaldehyde.

Organic functionalization of nanomaterials offers exceptional flexibility in materials design, and applications in molecular sensors and molecular electronics are expected. However, more studies should be conducted to understand the interaction between nanomaterials and organic molecules. In this work, we studied the functionalization of silicene and silicane with benzaldehyde, performing nudged elastic band calculations within density functional theory. We calculated the structural changes of the adsorption process, electronic properties of the main states, and the energetics. In silicene, the adsorption of benzaldehyde on the top site was found to be the most stable, with an adsorption energy of -0.55 eV. For silicane, the functionalization proceeds through a self-propagating reaction on a highly reactive dangling bond generated by a hydrogen atom vacancy. Benzaldehyde adsorbed on this site depicts an adsorption energy of -1.39 eV, which is larger than in bare silicene. Upon attaching, the double C=O bond breaks down turning the molecule into a highly reactive radical, which in this case, abstracts a neighboring H atom of the sheet. This process is highly achievable since the energy barrier to abstract the H atoms is 0.81 eV, whereas the one needed to desorb the molecule is 1.39 eV. After H abstraction, a new dangling bond is generated at the substrate, making a chain reaction possible to potentially form benzaldehyde monolayers. Organic functionalization is an excellent tool to engineer properties of 2D systems, and having a deeper understanding of the adsorption processes is the first step toward the development of new generation devices. Graphical abstract Benzaldehyde adsorbed on silicene and silicane.

N-Doped carbon nanotubes enriched with graphitic nitrogen in a buckypaper configuration as efficient 3D electrodes for oxygen reduction to H2O2.

Herein, a series of N-doped carbon nanotube (CNx) samples were obtained by modifying the synthesis temperature. Consequently, the proportion of graphitic nitrogen (Ngraph) in the samples was systematically increased as a function of temperature. This allowed evaluation of the role of the CNx graphitic nitrogen in the oxygen reduction reaction (ORR). A correlation between the Ngraph content and the ORR onset potential was observed, which shifted to more positive potentials with an increase in kinetic current density (jk); this showed that Ngraph played a significant catalytic role in the ORR. The samples with high Ngraph content favored the two-electron pathway for the ORR not only in basic media (pH = 13) but also in neutral media (pH = 7), representing an attractive alternative for wastewater remediation through the on-site generation of H2O2. The energetic calculations showed that the formation of H2O2 must be favorable in the presence of graphitic nitrogen sites. Finally, the performance of the buckypaper arrangement was evaluated, and the CNx buckypaper showed a higher cathodic current peak as compared to CNx traditional ink dispersions. Overall, this study not only sheds light on the role of Ngraph in the ORR, but also demonstrates that CNx buckypaper is an efficient 3D electrode for electrocatalytic applications.

Acetylene chain reaction on hydrogenated boron nitride monolayers: a density functional theory study.

Spin-polarized first-principles total-energy calculations have been performed to investigate the possible chain reaction of acetylene molecules mediated by hydrogen abstraction on hydrogenated hexagonal boron nitride monolayers. Calculations have been done within the periodic density functional theory (DFT), employing the PBE exchange correlation potential, with van der Waals corrections (vdW-DF). Reactions at two different sites have been considered: hydrogen vacancies on top of boron and on top of nitrogen atoms. As previously calculated, at the intermediate state of the reaction, when the acetylene molecule is attached to the surface, the adsorption energy is of the order of -0.82 eV and -0.20 eV (measured with respect to the energy of the non interacting molecule-substrate system) for adsorption on top of boron and nitrogen atoms, respectively. After the hydrogen abstraction takes place, the system gains additional energy, resulting in adsorption energies of -1.52 eV and -1.30 eV, respectively. These results suggest that the chain reaction is energetically favorable. The calculated minimum energy path (MEP) for hydrogen abstraction shows very small energy barriers of the order of 5 meV and 22 meV for the reaction on top of boron and nitrogen atoms, respectively. Finally, the density of states (DOS) evolution study helps to understand the chain reaction mechanism. Graphical abstract Acetylene chain reaction on hydrogenated boron nitride monolayers.

Albumin (BSA) adsorption onto graphite stepped surfaces.

Nanomaterials are good candidates for the design of novel components with biomedical applications. For example, nano-patterned substrates may be used to immobilize protein molecules in order to integrate them in biosensing units. Here, we perform long MD simulations (up to 200 ns) using an explicit solvent and physiological ion concentrations to characterize the adsorption of bovine serum albumin (BSA) onto a nano-patterned graphite substrate. We have studied the effect of the orientation and step size on the protein adsorption and final conformation. Our results show that the protein is stable, with small changes in the protein secondary structure that are confined to the contact area and reveal the influence of nano-structuring on the spontaneous adsorption, protein-surface binding energies, and protein mobility. Although van der Waals (vdW) interactions play a dominant role, our simulations reveal the important role played by the hydrophobic lipid-binding sites of the BSA molecule in the adsorption process. The complex structure of these sites, that incorporate residues with different hydrophobic character, and their flexibility are crucial to understand the influence of the ion concentration and protein orientation in the different steps of the adsorption process. Our study provides useful information for the molecular engineering of components that require the immobilization of biomolecules and the preservation of their biological activity.

Ab-initio study of ReCN in the bulk and as a new two dimensional material.

First principles total energy calculations have been applied to describe the ReCN bulk structure and the formation of ReCN monolayers and bilayers. Results demonstrate a strong structural rearrangement in the monolayer due to a reduced dimension effect: an increase in the lattice parameter, accompanied with the contraction of the distance between the C and N planes. On the other hand, a ReCN bilayer has structural parameters similar to those of the bulk. Surface formation energies show that the monolayer is more stable than bilayer geometries. Although bulk ReCN shows a semiconductor behavior, the monolayer ReCN presents a metallic behavior. This metallic character of the ReCN monolayer is mainly due to the d-orbitals of Re atoms.

Two-dimensional boron nitride structures functionalization: first principles studies.

Density functional theory calculations have been performed to investigate two-dimensional hexagonal boron nitride (2D hBN) structures functionalization with organic molecules. 2x2, 4x4 and 6x6 periodic 2D hBN layers have been considered to interact with acetylene. To deal with the exchange-correlation energy the generalized gradient approximation (GGA) is invoked. The electron-ion interaction is treated with the pseudopotential method. The GGA with the Perdew-Burke-Ernzerhoff (PBE) functionals together with van der Waals interactions are considered to deal with the composed systems. To investigate the functionalization two main configurations have been explored; in one case the molecule interacts with the boron atom and in the other with the nitrogen atom. Results of the adsorption energies indicate chemisorption in both cases. The total density of states (DOS) displays an energy gap in both cases. The projected DOS indicate that the B-p and N-p orbitals are those that make the most important contribution in the valence band and the H-s and C-p orbitals provide an important contribution in the conduction band to the DOS. Provided that the interactions of the acetylene with the 2D layer modify the structural and electronic properties of the hBN the possibility of structural functionalization using organic molecules may be concluded.