Valence Orbitals Research Articles

Soil elemental cycles become more coupled in response to increased nitrogen deposition in a semiarid shrubland

Abstract Background and aims Increased N deposition can break the coupled associations among chemical elements in soil, many of which are essential plant nutrients. We evaluated the effects of four years of N deposition (0, 10, 20, 50 kg N ha−1 yr−1) on the temporal dynamics of the spatial co-variation (i.e., coupling) among ten chemical elements in soils from a semiarid shrubland in central Spain. Methods Soil element coupling was calculated as the mean of Spearman rank correlation coefficients of all possible pairwise interactions among elemental cycles, in absolute value. We also investigated the role of atomic properties of elements as regulators of coupling. Results While N deposition impacts on nutrient bioavailability were variable, soil elemental coupling consistently increased in response to N. Coupling responses also varied among elements and N treatments, and four out of ten elemental cycles also responded to N in a season-dependent manner. Atomic properties of elements such as mass, valence orbitals, and electronegativity contributed to explain the spatial coupling of soil elements, most likely due their role on the capacity of elements to interact with one another. Conclusions The cumulative effects of N deposition can alter the spatial associations among chemical elements in soils, while not having evident consequences on the bioavailability of single elments. These results indicate that considering how multiple elements co-vary in topsoils may provide a useful framework to better understand the simultaneous response of multiple elemental cycles to global change.

Calculation of DC Stark Resonances for the Ammonia Molecule.

A model potential previously developed for the ammonia molecule is treated in a single-center partial-wave approximation in analogy with a self-consistent field method developed by Moccia. The latter was used in a number of collision studies. The model potential is used to calculate DC Stark resonance parameters, i.e., resonance positions and shifts using the exterior complex scaling method for the radial coordinate. Three molecular valence orbitals are investigated for fields along the three Cartesian coordinates, i.e., along the molecular axis and in two perpendicular directions. The work extends previous work on the planar-geometry water molecule for which non-monotonic shifts were observed. We find such non-monotonic shifts for fields along the molecular axis. For perpendicular fields, we report the splitting of the 1e orbitals into a fast- and a slow-ionizing orbital.

Photoionization of the Propargyl Radical Using the R-Matrix Method.

The absolute photoionization cross section of the propargyl radical measured by Savee et al. [J. Chem. Phys. 2012, 136, 134307] is about 2-3 times larger than the experimental result from Robinson et al. [J. Chem. Phys. 2003, 119, 5311]. Meanwhile, there is a significant discrepancy in the shapes of the propargyl photoionization spectra between these two measurements and the result measured by Zhang et al. [J. Chem. Phys. 2006, 124, 074302]. To estimate the accuracy of the various results, we carried out comprehensive calculations with the multichannel R-matrix method, which uses multiconfigurational wave functions to generate accurate initial and final states. Three scattering models including static-exchange, correlated 1 state, and 80 state close-coupling (CC) approximations are employed to reveal the dynamic interaction. The autoionization peaks near the ionization threshold are predicted for the first time. Two resonances are detected with the photon energy around 41.4 and 49.6 eV in the 80 state CC model. We checked the sensitivity of the results to change descriptions of the active spaces, the different partial waves, and the R-matrix radii in the theoretical model. Our best results are compared with the experimental measurements, and discussions are provided. The cross sections and asymmetry parameters for the valence orbitals are reported for photon energies from ionization thresholds of 70 eV.

Photoionization cross sections of Ethylene oxide

Abstract In this work a theoretical study for photoionization of Ethylene oxide is presented. The photoionization cross section (PICS) for each of the nine valence orbitals and also the summed cross sections are presented. Electronic structure calculations are done to obtain the required molecular properties and the Variational Schwinger method with Padé approximants is used to calculate the PICS. The results are shown in four different approaches: dipole-length/velocity form, static-exchange and static-exchange-polarization levels. The partial PICS for each orbital shows which symmetries of continuum states are responsible for resonance features and how the polarization effects affect the cross sections magnitudes near the threshold. PICS calculations indicate which parent ion state is generated according to the corresponding ionization energies. A correlation is proposed suggesting that the different ionic fragments can be preferentially produced by different electronic states of the parent ion, based on their ionic fragment appearance energies. The summed cross section of all valence orbitals of Ethylene oxide is compared with the results of Acetaldehyde and the analysis suggests that the PICSs, in a given energy range, can be used to identify these isomers. A comparison of our results for EtO and Acetaldehyde with available experimental results for Acetaldehyde and Ethenol demonstrated the the results of three isomers are similar in magnitude in the energy range from 9 to 12 eV. Furthermore, for acetaldehyde, we observed quantitative agreement with the experiment, indicating the reliability of our calculations.

Analysis of the Unusual Chemical Bonds and Dipole Moments of AeF- (Ae=Be-Ba): A Lesson in Covalent Bonding.

Quantum chemical calculations of the anions AeF- (Ae=Be-Ba) have been carried out using ab initio methods at the CCSD(T)/def2-TZVPP level and density functional theory employing BP86 with various basis sets. The detailed bonding analyses using different charge- and energy partitioning methods show that the molecules possess three distinctively different dative bonds in the lighter species with Ae=Be, Mg and four dative bonds when Ae=Ca, Sr, Ba. The occupied 2p atomic orbitals (AOs) and to a lesser degree the occupied 2s AO of F- donate electronic charge into the vacant spx(σ) and p(π) orbitals of Be and Mg which leads to a triple bond Ae F-. The heavier Ae atoms Ca, Sr, Ba use their vacant (n-1)d AOs as acceptor orbitals which enables them to form a second σ donor bond with F- that leads to quadruply bonded Ae F- (Ae=Ca-Ba). The presentation of molecular orbitals or charge distribution using only one isodensity value may give misleading information about the overall nature of the orbital or charge distribution. Better insights are given by contour line diagrams. The ELF calculations provide monosynaptic and disynaptic basins of AeF- which nicely agree with the analysis of the occupied molecular orbitals and with the charge density difference maps. A particular feature of the covalent bonds in AeF- concerns the inductive interaction of F- with the soft valence electrons in the (n)s valence orbitals of Ae. The polarization of the (n)s2 electrons induces a (n)spx hybridized lone-pair orbital at atom Ae, which yields a large dipole moment with the negative end at Ae. The concomitant formation of a vacant (n)spx AO of atom Ae, which overlaps with the occupied 2p(σ) AO of F-, leads to a strong covalent σ bond.

Evaluation of picture change effects on fractional occupation number states in noble gas atoms

In the two-component relativistic density functional theory, the picture change error (PCE), which originates from insufficient transformation of operators, should be corrected. In this study, we examine the PCE in the fractional occupation number (FON) state based on the spin-free infinite-order two-component Hamiltonian. The PCE for the total and orbital energy changes is estimated with respect to the FON electrons of the highest occupied molecular orbital and 1s core orbital in noble gas atoms. PCE is significant in core orbitals in heavy elements but relatively small in light elements and valence orbitals. The delocalization error, which can be represented by the total energy deviation from the behavior of the exact energy, is overestimated by the lack of picture change correction of the two-electron operator and underestimated by that of the density operator. Corresponding to these results, the PCE influences the value of orbital energies and slope of orbital energy change to FON.

Water Oxidation over Au-Pd/TiO2 as a Substitute for Iridium-Based Catalysts

Water oxidation is one of the most important reactions needed for a transition to a green economy. The reaction relies on extracting electrons from oxygen anions and is commonly studied using homogenous catalysts based on Ru or Ir metals. Because of Ir scarcity and its relative instability in acidic environments, metals to replace it are sought after. In this study, we have synthesized Au-Pd-based catalysts deposited on TiO2 with different ratios in order to mimic IrO2 valence orbitals (Ir5d) by the hybrid valence orbitals of Au5d and Pd4d and compared their heterogeneous catalytic activity for the evolution of O2 from water in the presence of cerium ammonium nitrate (CAN). Au-Pd-based catalysts were found to be active at a particular nominal atomic ratio. At an atomic ratio of 1 Au to 2 Pd and 1 Au to 3 Pd, the catalysts were active and stable for oxygen production from water. Long-term runs up to 20,000 min still showed the expected stoichiometry between O2 production and CAN consumption (1 to 4). However, catalysts with a reverse ratio were not active. Also, the monometallic catalysts were found to be not active for the reaction. We link the reason for the activity of Au-Pd with this specific ratio to the shape and energy position of their valence band that might be similar to those of IrO2 particles. While the turnover numbers of the Au-Pd-based catalysts were found to be lower than those of IrO2-based catalysts, on the same support in a heterogenous system, there is considerable potential upon further optimization for these two metals to replace IrO2 for a water oxidation reaction.

Carbon-Atom Exchange between [MC2]+ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects.

Gas-phase reactions of [OsC2]+ and [IrC2]+ with methane at ambient temperature have been studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Both [OsC2]+ and [IrC2]+ undergo carbon-atom exchange reactions with methane. The associated mechanisms for the two systems are found to be similar. The differences in the rates of carbon isotope exchange reactions of methane with [MC2]+ (M = Os and Ir) are explained by several factors like the energy barrier for the initial H3C-H bond breaking processes, the molecular dynamics, orbital interactions, and the H-binding energies of the pivotal steps. Besides, the number of participating valence orbitals might be one of the keys to regulate the rate in the key step. The present findings may provide useful ideas and inspiration for designing similar processes.

Density Functional Theory Investigation of Cu, Ni, and Ag Inclusion in ZSM-5 to Study Dihydrogen Binding for Cryogenic Molecular Sieve Bed Adsorber in Nuclear Fusion Systems

A computational investigation of Cu-, Ni-, and Ag-introduced ZSM-5 as potential hydrogen storage materials for nuclear fusion energy systems is performed. Among the 24 distinct tetrahedral sites of the monoclinic phase of ZSM-5, systematic periodic density functional theory (DFT) computations have been carried out on 15 experimentally identified T sites that show clear Al site preference and stability in high Si ZSM-5. Adsorption energies estimated from DFT studies have revealed that the T sites in the sinusoidal channels T4 and T10 are the most stable for including all three metal ions. Hence, these should also be considered as potential active sites for dihydrogen binding investigations in addition to the common T12 site in the intersection. The average hydrogen binding energies at these representative T sites were −79 to −45 kJ/mol, which correlates well with both the metal-H2 distance and H-H bond elongation distance. The computed hydrogen bond stretching frequency values were in the 3300 to 3755 cm−1 range upon adsorption of H2 onto the Ni, Cu, and Ag, indicating Kubas-type dihydrogen complex formation. The evidence for dihydrogen binding was also obtained from investigating the σ donation and back donation between the metal ion valence orbitals and the H2σ, H2σ* orbitals through projected density of states and natural bond order analysis. Our analysis indicates that Ni is better stabilized in the framework sites and is considered a potential candidate for dihydrogen binding.

Unusual quadruple bonds featuring collective interaction-type σ bonds between first octal-row atoms in the alkaline-earth compounds AeOLi2 (Ae = Be-Ba).

Quantum chemical calculations are reported for the complexes of alkaline earth metals AeOLi2 (Ae = Be-Ba) at the BP86-D3(BJ)/def2-QZVPP and CCSD(T)/def2-QZVPPQZVPP levels. The nature of the Ae-OLi2 bond has been analyzed with a variety of methods. The AeOLi2 molecules exhibit an unprecedented σ donor bond Ae→OLi2 where the (n)s2 lone-pair electrons of the Ae atom are donated to vacant O-Li2 antibonding orbitals having the largest coefficient at lithium. This is a covalent bond where the accumulation of the associated electronic charge is located at two positions above and below the Ae-OLi2 axis. The bifurcated component of orbital interactions is structurally related to the recently proposed collective bonding model, but exhibits a completely different type of bonding. The most stable isomer of AeOLi2 has a C 2v geometry and a singlet (1A1) electronic ground state. The bond dissociation energy (BDE) of the Ae-OLi2 bonds exhibits a zig-zag trend from BeOLi2 to BaOLi2, with BeOLi2 having the largest BDE (D e = 73.0 kcal mol-1) and MgOLi2 possessing the lowest BDE (D e = 42.3 kcal mol-1) at the CCSD(T) level. The calculation of the atomic partial charges by the Hirshfeld and Voronoi methods suggests that Be and Mg carry small negative charges in the lighter molecules whereas the heavier atoms Ca-Ba have small positive charges. In contrast, the NBO and QTAIM methods give positive charges for all Ae atoms that are larger for Ca-Ba than that calculated by the Hirshfeld and Voronoi approaches. The molecules AeOLi2 have large dipole moments where the negative end is at the Ae atom with the polarity Ae→OLi2. The largest dipole moments are predicted for the lighter species BeOLi2 and MgOLi2 and the smallest value is calculated for BaOLi2. The calculation of the vibrational spectra shows a significant red-shift toward lower wave numbers for the Ae-OLi2 stretching mode in comparison to diatomic AeO. Besides the Ae→OLi2 σ-donor bonds there are also three dative bonds due to Ae←OLi2 backdonation which consist of one σ bond and two π bonds. The appearance of strong Ae→OLi2 σ donation leads to quadruple bonds AeOLi2 in all systems AeOLi2, even for the lightest species with Ae = Be, Mg. The valence orbitals of Ca, Sr, and Ba, which are involved in the dative interactions, are the (n)s and (n-1)d AOs whereas Be and Mg use their (n)s and (n)p AOs. The EDA-NOCV results are supported by the AdNDP calculations which give four 2c-2e bonding orbitals. Three bonding orbitals have occupation numbers ∼2. One σ orbital has smaller occupation numbers between 1.32 and 1.73 due to the delocalization to the lithium atoms. The analysis of the electronic structure with the ELF method suggests multicenter bonds with mainly trisynaptic and tetrasynaptic basins, which also support the results of the EDA-NOCV calculations.

Enhancement of Parity-Violating Energy Difference of CHFClBr, CHFClI, and CHFBrI by Breaking the Cancellation among Valence Orbital Contributions

Enhancement of Parity-Violating Energy Difference of CHFClBr, CHFClI, and CHFBrI by Breaking the Cancellation among Valence Orbital Contributions

Molecular orbital tomography of HOMO and HOMO-1 of the nonlinear molecule H2O: The study on multi-orbital effects

Molecular orbital tomography (MOT) through high-order harmonic generation (HHG) is a crucial method for probing individual molecular orbitals. Previous studies mainly focused on linear molecules such as N2, and CO, where valence orbitals were imaged by detecting harmonic emission at various alignments. In this study, we investigate the HHG from the water molecules, with the aim of exploring MOT for nonlinear molecules. By employing the time-dependent density functional theory, we obtain HHG spectra for different angles between the laser polarization and molecular symmetry axis. By manipulating the scanning planes (planes perpendicular to the laser propagation direction and contain the field polarization direction), specific orbitals can be selectively imaged. Particularly, a well-reconstructed highest occupied molecular orbital (HOMO) is obtained when the laser scanning plane approximately aligns with the nodal plane of HOMO-1. However, when the laser polarization deviates from the nodal plane, multiple orbitals contribute to the HHG process, and we visualize the orbital distortions resulting from such effects. Furthermore, HOMO-1, can be reconstructed when the laser scanning plane aligns with the nodal plane of HOMO. This research significantly advances the development of MOT and opens up intriguing possibilities for reconstructing orbitals of more complex molecules.

Symmetry and Electronic Properties of Metallic Nanoclusters

Spherical nanoclusters with countable member atoms and delocalized valence orbitals are superatoms with properties analogous to those of simple atoms. This is reflected, in particular, in their optical spectra and magnetic properties, in a similar sense to transition metal ions and complexes. Clusters can be of low-spin or high-spin with considerable contributions to magnetism by the large cluster orbital magnetic moment. Due to the large radius of the clusters, they can be diamagnetic with an unusually high diamagnetic susceptibility. Gold and platinum, which in the bulk are non-magnetic, show pronounced superparamagnetism associated with their high-spin nature, and the magnetic moment can be trapped in symmetry-breaking environments so that hysteresis pertains far beyond room temperature. A significant deviation from hydrogen-like orbitals results from the shape of the confining potential, which has the effect that the orbital quantum number ℓ is not limited to values less than the principal quantum number n.

A Comparison between Triphenylmethyl and Triphenylsilyl Spirobifluorenyl Hosts: Synthesis, Photophysics and Performance in Phosphorescent Organic Light-Emitting Diodes.

This study presents the synthesis and characterization of two spirobifluorenyl derivatives substituted with either triphenylmethyl (SB-C) or triphenylsilyl (SB-Si) moieties for use as host materials in phosphorescent organic light-emitting diodes (PHOLED). Both molecules have similar high triplet energies and large energy gaps. Blue Ir(tpz)3 and green Ir(ppy)3 phosphorescent devices were fabricated using these materials as hosts. Surprisingly, SB-Si demonstrated superior charge-transporting ability compared to SB-C, despite having similar energies for their valence orbitals. In particular, SB-Si proved to be a highly effective host for both blue and green devices, resulting in maximum efficiencies of 12.6% for the Ir(tpz)3 device and 9.6% for the Ir(ppy)3 device. These results highlight the benefits of appending the triphenylsilyl moiety onto host materials and underscore the importance of considering the morphology of hosts in the design of efficient PHOLEDs.

Bonding Analysis of the Ge‐Ge Bonds in the Octagermacubane Ge8(Sit‐butyl2methyl)6

AbstractQuantum chemical calculations have been carried out at the BP86/def2‐SVP level on Ge8(Sit‐butyl2methyl)6(1) and the bonding situation has been analyzed with a variety of methods. The calculated equilibrium geometry of1is in good agreement with the reported x‐ray structure analysis. The D3 correction for dispersion interactions as a sum of pairwise attractions leads to an overestimate of the effect of dispersion forces. Calculations at BP86‐D3(BJ)/def2‐SVP give shorter bonds for Ge(I)−Ge(I) than for Ge(0)−Ge(I), which is in contrast to the experimental values and the BP86/def2‐SVP results. The NBO analysis suggests that the best Lewis structure of1has lone‐pair orbitals at the Ge(0) atoms with occupation numbers of 1.70 e. A lone‐pair character at Ge(0) albeit with less weight is also suggested by the shape of the HOMO, which is an antibonding orbital between the Ge(0) atoms with small contributions from the Ge(I) atoms. The LUMO of1is the corresponding bonding combination of the Ge(0) AOs, which can be explained with the reluctance of the heavier main‐group atoms to s/p hybridization of the valence orbitals. The calculated bond order values suggest significant direct Ge(0)−Ge(0) interactions. This is supported by the shape of the HOMO and by the results of EDA‐NOCV calculations. The deformation densities and the orbitals associated with the pairwise orbital interaction show that there is a direct charge flow between the Ge(0) atoms of the two fragments, but it is not completely separated from the Ge(0)−Ge(I) and Ge(I)−Ge(I) bond formation. The QTAIM calculations suggest that1has a cubic structure with a cage critical point but not a bond critical point for the Ge(0)−Ge(0) interactions. The dispersion interactions of the large substituents in1have a significant influence on the stability of the compound.

Uncovering the 3d and 4d Electronic Interactions in Solvated Ru Complexes with 2p3d Resonant Inelastic X-ray Scattering.

The electronic structure and dynamics of ruthenium complexes are widely studied given their use in catalytic and light-harvesting materials. Here we investigate three model Ru complexes, [RuIII(NH3)6]3+, [RuII(bpy)3]2+, and [RuII(CN)6]4-, with L3-edge 2p3d resonant inelastic X-ray scattering (RIXS) to probe unoccupied 4d valence orbitals and occupied 3d orbitals and to gain insight into the interactions between these levels. The 2p3d RIXS maps contain a higher level of spectral information than the L3 X-ray absorption near edge structure (XANES). This study provides a direct measure of the 3d spin-orbit splittings of 4.3, 4.0, and 4.1 eV between the 3d5/2 and 3d3/2 orbitals of the [RuIII(NH3)6]3+, [RuII(bpy)3]2+, and [RuII(CN)6]4- complexes, respectively.

Band structures and Z2 invariants of two-dimensional transition metal dichalcogenide monolayers from fully relativistic Dirac-Kohn-Sham theory using Gaussian-type orbitals

Two-dimensional (2D) materials exhibit a wide range of remarkable phenomena, many of which owe their existence to the relativistic spin-orbit coupling (SOC) effects. To understand and predict properties of materials containing heavy elements, such as the transition-metal dichalcogenides (TMDs), relativistic effects must be taken into account in first-principles calculations. We present an all-electron method based on the four-component Dirac Hamiltonian and Gaussian-type orbitals (GTOs) that overcomes complications associated with linear dependencies and ill-conditioned matrices that arise when diffuse functions are included in the basis. Until now, there has been no systematic study of the convergence of GTO basis sets for periodic solids either at the nonrelativistic or the relativistic level. Here we provide such a study of relativistic band structures of the 2D TMDs in the hexagonal (2H), tetragonal (1T), and distorted tetragonal (1T') structures, along with a discussion of their SOC-driven properties (Rashba splitting and $\mathbb{Z}_2$ topological invariants). We demonstrate the viability of our approach even when large basis sets with multiple basis functions involving various valence orbitals (denoted triple- and quadruple-$\zeta$) are used in the relativistic regime. Our method does not require the use of pseudopotentials and provides access to all electronic states within the same framework. Our study paves the way for direct studies of material properties, such as the parameters in spin Hamiltonians, that depend heavily on the electron density near atomic nuclei where relativistic and SOC effects are the strongest.

Tailoring Ti3C2 MXene into Ti3C2Tx, Tx = NO and alloying with M = Al, Ga, In, Tl into MTi3C2NO as electrode materials for super-capacitor devices: Perspective from first-principles density functional theory

Theoretical calculations using a density functional theory (DFT) approach has been utilized to explore the structural, electronic, and optical properties of Ti3C2, Ti3C2Tx, Tx = NO, and its alloys with Group IIIA elements (Al, Ga, In, Tl) as electrode materials for supercapacitor devices. The results show good crystal stability and an increase in the metallic property of the functionalized/alloyed MXenes (Ti3C2NO, AlTi3C2NO, GaTi3C2NO, InTi3C2NO, and Tl Ti3C2NO) making them better candidates for application as electrode materials. The band structures of the studied compounds revealed a direct band interaction and a progressive increase in the overlap of the bands upon introducing the terminating group (NO) and when alloyed with Al, Ga, In, and Tl. The partial and total density of states of the studied compounds confirmed their metallic behaviour and conductivity. The spin-polarized band structures and spin-polarized DOS of the compounds studied have revealed their antiferromagnetic properties, while TlTi3C2NO showed an interesting non-collinear spin-polarized structure, which is indicative of a great Nerst effect. Our density of states calculations demonstrates a good interaction was formed in the valence orbitals of the studied compounds with a Fermi level of 0 eV, which is indicative of a good conductor and a metallic character. The quantum capacitance of the studied compounds (MXenes) revealed an improved QC upon surface functionalization and alloying with the obtained MXenes QC values as follows: Ti3C2 = 97.5 μF/cm2, AlTi3C2NO = 141.8 μF/cm2, InTi3C2NO = 142.5 μF/cm2, and TlTi3C2NO = 100.5 μF/cm2, which are good QC values for potential electrode materials, while GaTi3C2NO = 7.5 μF/cm2. Our optical studies revealed the good interaction between the MXenes and electromagnetic waves. The MXenes exhibit good dielectric permeability, as the real parts Ꜫr(ω) of the dielectric function is ≥ 19. The imaginary parts Ꜫz(ω) of the dielectric function revealed peaks with intensity >100, which are indicative of inter-band transition.

Unexpected d–p orbital covalent interaction between the non-d-block main-group metal tellurium and fluorine at high pressure

As a 5p-block main-group metal, tellurium generally loses its outermost electrons and forms ionic compounds upon encountering more electronegative elements under ambient conditions. Here, we report an unexpected d–p orbital covalent interaction between the 5p-block metal tellurium and the most electronegative element F at high pressure. In tellurium fluorides, the strong fluorine ligand field affects the effective nuclear charge of the metal atom and then affects the valence orbital energies of the central tellurium atom, incorporating unoccupied 5d orbitals of tellurium into the valence orbitals and interacting strongly with the valence orbitals of F atoms under high pressure. An electronic structure analysis of tellurium fluorides reveals the existence of strong d–p covalent interactions in the Te−F system. This study is extremely valuable for advancing our understanding of chemical bonding and high-pressure main-group chemistry.

Electronic structure alteration in MgO monolayer through alkali metal doping

We have studied the structural and electronic properties of MgO monolayer (ML) by substituting one of its Mg sites with alkali metal atoms (Li, Na, K) using DFT calculations in Quantum ESPRESSO. All the planar-doped monolayers are structurally stable shown by the computed binding energy per atom values. Formation energies suggest that Li exhibits the strongest binding with MgO ML. Doping turns the non-magnetic semiconducting MgO MLs into half-metallic magnets with magnetic moment of ∼ 1μB. The corresponding magnetic states are contributed by the valence orbitals of O atoms near the doping sites. Thus, Li, Na, K substitution introduces huge changes in electronic structure and properties of MgO ML.