Feasibility of dose calculation for treatment plans using electron density maps from a novel dual-layer detector spectral CT simulator.

BACKGROUND: Conventional single-energy CT can only provide a raw estimation of electron density (ED) for dose calculation by developing a calibration curve that simply maps the HU values to ED values through their correlations. Spectral CT, also known as dual-energy CT (DECT) or multi-energy CT, can generate a series of quantitative maps, such as ED maps. Using spectral CT for radiotherapy simulations can directly acquire ED information without developing specific calibration curves. The purpose of this study is to assess the feasibility of utilizing electron density (ED) maps generated by a novel dual-layer detector spectral CT simulator for dose calculation in radiotherapy treatment plans. METHODS: 30 patients from head&neck, chest, and pelvic treatment sites were selected retrospectively, and all of them underwent spectral CT simulation. Treatment plans based on conventional CT images were transplanted to ED maps with the same structure set, including planning target volume (PTV) and organs at risk (OARs), and the dose distributions were then recalculated. The differences in dose and volume histogram (DVH) parameters of the PTV and OARs between the two types of plans were analyzed and compared. Besides, gamma analysis between these plans was performed by using MEPHYSTO Navigator software. RESULTS: In terms of PTV, the homogeneity index (HI), gradient index (GI), D2%, D98%, and Dmean showed no significant difference between conventional plans and ED plans. For OARs, statistically significant differences were observed in parotids D50%, brainstem in head&neck plans, spinal cord in chest plans and rectum D50% in pelvic plans, whereas the variance remained minor. For the rest, the DVH parameters exhibited no significant difference between conventional plans and ED plans. All of the mean gamma passing rates (GPRs) of gamma analysis were higher than 90%. CONCLUSION: Compared to conventional treatment plans relying on CT images, plans utilizing ED maps demonstrated similar dosimetric quality. However, the latter approach enables direct utilization in dose calculation without the requirements of establishing and selecting a specific Hounsfield unit (HU) to ED calibration curve, providing an advantage in clinical applications.

Evolution of structural and electronic properties standardized description in rhenium disulfide at the bulk-monolayer transition.

The structural and electronic properties of ReS2 different forms - three-dimensional bulk and two-dimensional monolayer - were studied within density functional theory and pseudopotentials. A method for standardizing the description of bulk unit cells and "artificial" slab unit cells for DFT research has been proposed. The preference of this method for studying zone dispersion has been shown. The influence of the vacuum layer thickness on specified special high-symmetry points is discussed. Electron band dispersion in both classical 3D Brillouin zones and transition to 2D Brillouin zones in the proposed two-dimensional approach using the Niggli form of the unit cell was compared. The proposed two-dimensional approach is preferable for low-symmetry layered crystals such as ReS2. It was established that the bulk ReS2 is a direct gap semiconductor (band gap of 1.20 eV), with the direct transition lying in the X point of the first Brillouin zone, and it is in good agreement with published experimental data. The reduction in material dimension from bulk to monolayer was conducted with an increasing band gap up to 1.45 eV, with a moving direct transition towards the Brillouin zone center. The monolayer of ReS2 is a direct-gap semiconductor in a wide range of temperatures, excluding only a narrow range at low temperatures, where it comes as a quasi-direct gap semiconductor. The transition, situated directly in the Γ-point, lies 3.3 meV below the first direct transition located near this point. The electronic density of states of ReS2 in the bulk and monolayer cases of ReS2 were analyzed. The molecular orbitals were built for both types of ReS2 structures as well as the electron difference density maps. For all types of ReS2 structures, an analysis of populations according to Mulliken and Voronoi was carried out. All calculated data is discussed in the context of weak quantum confinement in the 2D case.

Analysis of the Electron Density of a Water Molecule Encapsulated by Two Cholic Acid Residues.

Cholic acid is a trihydroxy bile acid with a nice peculiarity: the average distance between the oxygen atoms (O7 and O12) of the hydroxy groups located at C7 and C12 carbon atoms is 4.5 Å, a value which perfectly matches with the O/O tetrahedral edge distance in Ih ice. In the solid phase, they are involved in the formation of hydrogen bonds with other cholic acid units and solvents. This fact was satisfactorily used for designing a cholic dimer which encapsulates one single water molecule between two cholic residues, its oxygen atom (Ow) being exactly located at the centroid of a distorted tetrahedron formed by the four steroid hydroxy groups. The water molecule participates in four hydrogen bonds, with the water simultaneously being an acceptor from the 2 O12 (hydrogen lengths are 2.177 Å and 2.114 Å) and a donor towards the 2 O7 (hydrogen bond lengths are 1.866 Å and 1.920 Å). These facts suggest that this system can be a nice model for the theoretical study of the formation of ice-like structures. These are frequently proposed to describe the water structure found in a plethora of systems (water interfaces, metal complexes, solubilized hydrophobic species, proteins, and confined carbon nanotubes). The above tetrahedral structure is proposed as a reference model for those systems, and the results obtained from the application of the atoms in molecules theory are presented here. Furthermore, the structure of the whole system allows a division into two interesting subsystems in which water is the acceptor of one hydrogen bond and the donor of another. The analysis of the calculated electron density is performed through its gradient vector and the Laplacian. The calculation of the complexation energy used correction of the basis set superposition error (BSSE) with the counterpoise method. As expected, four critical points located in the H…O bond paths were identified. All calculated parameters obey the proposed criteria for hydrogen bonds. The total energy for the interaction in the tetrahedral structure is 54.29 kJ/mol, while the summation obtained of the two independent subsystems and the one between the alkyl rings without water is only 2.5 kJ/mol higher. This concordance, together with the calculated values for the electron density, the Laplacian of the electron density, and the lengths of the oxygen atom and the hydrogen atom (involved in the formation of each hydrogen bond) to the hydrogen bond critical point, suggests that each pair of hydrogen bonds can be considered independent of each other.

Compositionally Complex Alloys: Some Insights from Photoemission Spectroscopy.

Photoemission spectroscopy (PES) is an underrepresented part of current and past studies of compositionally complex alloys (CCA) such as high-entropy alloys (HEA) and their derivatives. PES studies are very important for understanding the electronic structure of materials, and are therefore essential in some cases for a correct description of the intrinsic properties of CCAs. Here, we present several examples showing the importance of PES. First, we show how the difference between the split-band structure and the common-band structure of the valence band (VB), observed by PES, can explain a range of properties of CCAs and alloys in general. A simple description of the band crossing in CCAs composed from the early and late transition metals showing a split band is discussed. We also demonstrate how a high-accuracy PES study can determine the variation in the density of states at the Fermi level as a function of Cu content in Ti-Zr-Nb-Ni-Cu metallic glasses. Finally, the first results of an attempt to single out the contributions of particular constituents in Cantor-type alloys to their VBs are presented. The basic principles of PES, the techniques employed in studies presented, and some issues associated with PES measurements are also described.

Vacancy-Rich MXene-Immobilized Ni Single Atoms as a High-Performance Electrocatalyst for the Hydrazine Oxidation Reaction.

Single-atom catalysts (SACs), on account of their outstanding catalytic potential, are currently emerging as high-performance materials in the field of heterogeneous catalysis. Constructing a strong interaction between the single atom and its supporting matrix plays a pivotal role. Herein, Ti3 C2 Tx -MXene-supported Ni SACs are reported by using a self-reduction strategy via the assistance of rich Ti vacancies on the Ti3 C2 Tx MXene surface, which act as the trap and anchor sites for individual Ni atoms. The constructed Ni SACs supported by the Ti3 C2 Tx MXene (Ni SACs/Ti3 C2 Tx ) show an ultralow onset potential of -0.03 V (vs reversible hydrogen electrode (RHE)) and an exceptional operational stability toward the hydrazine oxidation reaction (HzOR). Density functional theory calculations suggest a strong coupling of the Ni single atoms and their surrounding C atoms, which optimizes the electronic density of states, increasing the adsorption energy and decreasing the reaction activation energy, thus boosting the electrochemical activity. The results presented here will encourage a wider pursuit of 2D-materials-supported SACs designed by a vacancy-trapping strategy.

Simulation and Computer Study of Structures and Physical Properties of Hydroxyapatite with Various Defects.

Simulation and computer studies of the structural and physical properties of hydroxyapatite (HAP) with different defects are presented in this review. HAP is a well-known material that is actively used in various fields of medicine, nanotechnology, and photocatalytic processes. However, all HAP samples have various defects and are still insufficiently studied. First of all, oxygen and OH group vacancies are important defects in HAP, which significantly affect its properties. The properties of HAP are also influenced by various substitutions of atoms in the HAP crystal lattice. The results of calculations by modern density functional theory methods of HAP structures with these different defects, primarily with oxygen and hydroxyl vacancies are analyzed in this review. The results obtained show that during the structural optimization of HAP with various defects, both the parameters of the crystallographic cells of the HAP change and the entire band structure of the HAP changes (changes in the band gap). This affects the electronic, optical, and elastic properties of HAP. The review considers the results of modeling and calculation of HAP containing various defects, the applied calculation methods, and the features of the effect of these defects on the properties of HAP, which is important for many practical applications.

The Neglected Nuclei.

Since the nuclei in a molecule are treated as stationary, it is perhaps natural that interpretations of molecular properties and reactivity have focused primarily upon the electronic density distribution. The role of the nuclei has generally received little explicit consideration. Our objective has been to at least partially redress this imbalance in emphasis. We discuss a number of examples in which the nuclei play the determining role with respect to molecular properties and reactive behavior. It follows that conventional interpretations based solely upon electronic densities and donating or withdrawing tendencies should be made with caution.

Ligand-Modified Boron-Doped Diamond Surface: DFT Insights into the Electronic Properties of Biofunctionalization.

With the increasing power of computation systems, theoretical calculations provide a means for quick determination of material properties, laying out a research plan, and lowering material development costs. One of the most common is Density Functional Theory (DFT), which allows us to simulate the structure of chemical molecules or crystals and their interaction. In developing a new generation of biosensors, understanding the nature of functional linkers, antibodies, and ligands become essential. In this study, we used DFT to model a bulk boron-doped diamond slab, modified by a functional linker and a surrogate proteins ligand. DTF calculations enable the prediction of electronic transport properties in an electrochemical sensor setup, composed of a boron-doped diamond electrode functionalized by 4-amino benzoic acids and a target surrogated protein-ligand for influenza. Electron conduction pathways and other signatures associated with the detection and measurement of the target analyte are revealed.

Largely Enhanced Seebeck Coefficient and Thermoelectric Performance by the Distortion of Electronic Density of States in Ge2Sb2Te5.

As one of the state-of-the-art phase-change materials, the stable Ge2Sb2Te5 hexagonal compound also exhibits decent thermoelectric performance with high electrical conductivity and low thermal conductivity. Nonetheless, the excessively high carrier concentration and low Seebeck coefficient are the bottlenecks to achieve high zT values. In this work, with the intention to optimize the electrical properties, indium was introduced as a potentially donor-like dopant in a series of Ge2-xInxSb2Te5 samples. The substitution of indium for germanium lowers the density of hole carriers and enhances the Seebeck coefficient. Noticeably, the room-temperature Seebeck coefficient of the doped samples can be three times as large as that of the pristine one, which obviously departures from the theoretically predicted Pisarenko relation based on the single parabolic band model. By virtue of DFT calculations and modeling, the remarkable enhancement of Seebeck coefficient was attributed to the doping-induced local distortion in the electronic density of states. Further insight reveals that indium doping amplifies the bonding character of Ge-Te adjacent to indium and enhances the atomic interaction along the c-axis. Due to the optimized electrical properties as well as the suppressed thermal conductivity, a maximal zT value of 0.78 was achieved in Ge1.85In0.15Sb2Te5 at 700 K, which is about 40% higher than that of the pristine sample.

Electronic Property and Negative Thermal Expansion Behavior of Si136-xGex (x = 8, 32, 40, 104) Clathrate Solid Solution from First Principles.

We present the electronic and vibrational studies on Si136-xGex (x = 8, 32, 40, 104) alloys, using the local density approximation (LDA) scheme. We find that a "nearly-direct" band gap exists in the band structure of Si104Ge32 and Si96Ge40, when compared with the similarly reported results obtained using a different computational code. The calculated electronic density of state (EDOS) profiles for the valence band remain nearly identical and independent of the Ge concentration (x = 32, 40, 104) even though some variation is found in the lower conduction band (tail part) as composition x is tuned from 8 (or 40) to 104. The negative thermal expansion (NTE) phenomenon is explored using quasi-harmonic approximation (QHA), which takes the volume dependence of the vibrational mode frequencies into consideration, while neglecting the temperature effect on phonon anharmonicity. Determined macroscopic Grüneisen parameter trends show negative values in the low temperature regime (1 K < T < 115 K), indicating the NTE behavior found in Si128Ge8 is analogous to the experimental result for Si136. Meanwhile, calculations for the ratio of the vibrational entropy change to the volume change at several characteristic temperatures reconfirm the existence of NTE in Si128Ge8 and Si104Ge32.

Linear σ-hole⋯CO⋯σ-hole intermolecular interactions between carbon monoxide and dihalogen molecules XY (X, Y=Cl, Br).

Carbon monoxide can interact with two dihalogen molecules XY (X, Y=Cl, Br) in the form of X(Y)⋯COX(Y)⋯CO⋯X(Y)X(Y) trimeric complex, and their nature and characteristics were investigated at MP2/aug-cc-pVDZ level without and with counterpoise method, together with single point calculations at CCSD(T)/aug-cc-pVDZ level. The optimized geometries, stretching modes and interaction energies of a series of X(Y)⋯COX(Y)⋯CO⋯X(Y)X(Y) trimeric complexes were obtained and discussed. The cooperativity in these complexes was evaluated. EDA analyses reveal that the electrostatic interaction is the dominant net driving force in each trimer, but the contributions of other interactions like exchange, dispersion and polarization interactions are also important. QTAIM and NCI analyses confirm the existence of attractive halogen-bonding interactions. Additionally, EDDMF analysis was employed for the component dimers of these trimers, which indicates that the formation of halogen-bonding interactions is closely related to the charge shift and the rearrangement of electronic density in the formation of these complexes. The results would provide valuable insight into for these linear halogen bonds.

Methylenecyclopropene: local vision of the first 1B2 excited state.

The 1A1 ground and the first 1B2 excited states of the methylenecyclopropene (triafulvene) are described by localized wave functions, based on 20 structures valence bond structures. The results are compared to CASSCF(4,4) calculations for both the energetics and the dipole moment. Additional calculations with partial electronic delocalization are presented, and it is shown that the dipole moment modification does not correspond to a situation where the antiaromatic situation prevails (with 4n electrons in the cycle). Part of the analysis uses a "trust factor" that helps to decide if a wave function is appropriate to describe a given state. The trust factor compares the VB wave function to the CASSCF's with their overlap. Finally, the valence bond density is used to produce density maps that illustrate the electron transfer upon excitation. Graphical Abstract A projector-based method compares CASSCF wave functions to local wave functions, including Lewis structures as shown in the picture. A "trust factor" (τ) is obtained. Both the ground state and the first excited state of the methylenecyclopropene are discussed.

Formation of Silicene Nanosheets on Graphite.

The extraordinary properties of graphene have spurred huge interest in the experimental realization of a two-dimensional honeycomb lattice of silicon, namely, silicene. However, its synthesis on supporting substrates remains a challenging issue. Recently, strong doubts against the possibility of synthesizing silicene on metallic substrates have been brought forward because of the non-negligible interaction between silicon and metal atoms. To solve the growth problems, we directly deposited silicon on a chemically inert graphite substrate at room temperature. Based on atomic force microscopy, scanning tunneling microscopy, and ab initio molecular dynamics simulations, we reveal the growth of silicon nanosheets where the substrate-silicon interaction is minimized. Scanning tunneling microscopy measurements clearly display the atomically resolved unit cell and the small buckling of the silicene honeycomb structure. Similar to the carbon atoms in graphene, each of the silicon atoms has three nearest and six second nearest neighbors, thus demonstrating its dominant sp2 configuration. Our scanning tunneling spectroscopy investigations confirm the metallic character of the deposited silicene, in excellent agreement with our band structure calculations that also exhibit the presence of a Dirac cone.

Electronic specific heats for amorphous and crystallized alloys.

The low temperature specific heats of (Fe0.5Co0.5)72B20Si4Nb4 amorphous and crystallized alloys are measured and analyzed from 1.4 to 110 K. Specific heats can be well fitted by electronic and phonon contribution terms. It is found that the electronic contribution term in specific heat for amorphous alloy is larger than that for crystallized one, and this phenomenon has been interpreted in detail. The research shows that the electronic density of states at the Fermi level and the localized loose "rattler" atoms in oversized cage structure may make contributions to the enhancement of electronic specific heat coefficient γ, and result in a larger electronic contribution term. This study is significant for further understanding the structure-property relationship for amorphous alloys at low temperature.

Trapping and Characterization of a Single Hydrogen Molecule in a Continuously Tunable Nanocavity.

Using inelastic electron tunneling spectroscopy with the scanning tunneling microscope (STM-IETS) and density functional theory calculations (DFT), we investigated properties of a single H2 molecule trapped in nanocavities with controlled shape and separation between the STM tip and the Au (110) surface. The STM tip not only serves for the purpose of characterization, but also is directly involved in modification of chemical environment of molecule. The bond length of H2 expands in the atop cavity, with a tendency of dissociation when the gap closes, whereas it remains unchanged in the trough cavity. The availability of two substantially different cavities in the same setup allows understanding of H2 adsorption on noble metal surfaces and sets a path for manipulating a single chemical bond by design.

Investigation of VO-salophen complexes electronic structure.

Vanadyl N,N'-bis(salicylidene)-o-phenylenediamine (salophen) complexes have been extensively investigated by cyclic voltammetry, UV-visible spectroscopy and theoretical calculations in MeCN, THF (tetrahydrofuran) and DMF (N,N-dimethylformamide), in order to elucidate the overall factors that influence the electronic density of the metal and therefore the properties of these complexes in various applications. Different substituents were introduced into the salophen skeleton to change the vanadium electron density. Results obtained and here presented showed that the substituents influence the metal electronic character in a way that cannot be easily predicted by considering only the electronic effect. Similarly, the solvent polarity or coordination ability affects the metal complex properties in an unpredictable way. Therefore, experimental and theoretical data here collected are a powerful tool to a priori design salophen ligands to obtain vanadyl complexes having the specific electronic properties suitable for desired applications.

The Ce2Li0.39Ni1.61Si2 structure as a new derivative of the AlB2 family.

A new quaternary dicerium lithium/nickel disilicide, Ce2Li0.39Ni1.61Si2, crystallizes as a new structure type of intermetallic compounds closely related to the AlB2 family. The crystal-chemical interrelationships between parent AlB2-type, BaLiSi, ZrBeSi and the title compound are discussed using the Bärnighausen formalism. Two Ce atoms occupy sites of 3m. symmetry. The remainder, i.e. Ni, mixed Ni/Li and Si atoms, occupy sites of -6m2 symmetry. The environment of the Ce atom is an 18-vertex polyhedron and the Ni, Ni/Li and Si atoms are enclosed in tricapped trigonal prisms. The title structure can be assigned to class No. 10 (trigonal prism and its derivatives) according to the Krypyakevich classification scheme [Krypyakevich (1977). In Structure Types of Intermetallic Compounds. Moscow: Nauka]. The electronic structure of the title compound was calculated using the tight-binding linear muffin-tin orbital method in the atomic spheres approximation (TB-LMTO-ASA). Metallic bonding is dominant in this compound. The strongest interactions are Ni-Si and Ce-Si.

Terthiophene on Au(111): A scanning tunneling microscopy and spectroscopy study.

Terthiophene (3T) molecules adsorbed on herringbone (HB) reconstructed Au(111) surfaces in the low coverage regime were investigated by means of low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) under ultra-high vacuum conditions. The 3T molecules adsorb preferentially in fcc regions of the HB reconstruction with their longer axis oriented perpendicular to the soliton walls of the HB and at maximum mutual separation. The latter observation points to a repulsive interaction between molecules probably due to parallel electrical dipoles formed during adsorption. Constant-separation (I-V) and constant-current (z-V) STS clearly reveal the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals, which are found at -1.2 eV and +2.3 eV, respectively. The HOMO-LUMO gap corresponds to that of a free molecule, indicating a rather weak interaction between 3T and Au(111). According to conductivity maps, the HOMO and LUMO are inhomogeneously distributed over the adsorbed 3T, with the HOMO being located at the ends of the linear molecule, and the LUMO symmetrically with respect to the longer axis of the molecule at the center of its flanks. Analysis of spectroscopic data reveals details of the contrast mechanism of 3T/Au(111) in STM. For that, the Shockley-like surface state of Au(111) plays an essential role and appears shifted outwards from the surface in the presence of the molecule. As a consequence, the molecule can be imaged even at a tunneling bias within its HOMO-LUMO gap. A more quantitative analysis of this detail resolves a previous discrepancy between the fairly small apparent STM height of 3T molecules (1.4-2.0 nm, depending on tunneling bias) and a corresponding larger value of 3.5 nm based on X-ray standing wave analysis. An additionally observed linear decrease of the differential tunneling barrier at positive bias when determined on top of a 3T molecule is compared to the bias independent barrier obtained on bare Au(111) surfaces. This striking difference of the barrier behavior with and without adsorbed molecules is interpreted as indicating an adsorption-induced dimensionality transition of the involved tunneling processes.

Relevance of Knight Shift Measurements to the Electronic Density of States.

The Knight shift, K , measures the magnetic hyperfine field at the nucleus produced by the conduction electrons which are polarized in a magnetic field. Knight shifts are often dominated by the Pauli term and, in its most simple form, can be written as K = 〈 a 〉 χ p . Here χ p is the conduction electron Pauli spin susceptibility which depends on the density of states at the Fermi level, N(E f ), and 〈a〉 is an average magnetic hyperfine coupling constant associated with the wave function character at the nucleus, ∣ψ F (0)∣2, for conduction electrons at the Fermi surface. The Knight shift therefore provides, through 〈a〉, insight into the wave-function character associated with N(E F ). Calculations of 〈a〉 involving an averaging over k-space have been attempted for a few simple metals up to the present time. For alloys and intermetallic compounds, rather different 〈a〉's are experimentally observed for different local environments, indicating that K samples the variation in local wave-function character, or a variation in local density of states. There is no unique way of separating the local variation of N(E F ) from ∣ψ F ∣(0)∣2. In this article the methods developed for relating K to the electronic properties for most of the types of cases encountered in the literature are reviewed. We discuss "simple" metals including problems of orbital magnetism and changes in K caused by electronic transitions such as melting. Knight shifts and their temperature dependence in metals and intermetallic compounds involving unfilled d shells, are discussed. We give estimates of atomic hyperfine fields due to single electrons, appropriate to those cases where problems due to electronic configurations do not make deductions from experiment too ambiguous. A density of states curve calculated for Cu is given, showing the relative importance of s-p, and d character for that metal. In a qualitative sense this Cu curve implies such information for other transition metals. We discuss alloy solid solutions for the cases where a "rigid" band model might be used to explain the results, and for cases where local effects have to be taken into account. The charge oscillation and RKKY approaches and their limitations are reviewed for cases of dilute nonmagnetic and d- or f-type impurities.