Effect of Alkali Metal Atoms Doping on Structural and Nonlinear Optical Properties of the Gold-Germanium Bimetallic Clusters.
ABSTRACT: A new series of alkali-based complexes, AM@GenAu (AM = Li, Na, and K), have been theoretically designed and investigated by means of the density functional theory calculations. The geometric structures and electronic properties of the species are systematically analyzed. The adsorption of alkali metals maintains the structural framework of the gold-germanium bimetallic clusters, and the alkali metals prefer energetically to be attached on clusters' surfaces or edges. The high chemical stability of Li@Ge12Au is revealed by the spherical aromaticity, the hybridization between the Ge atoms and Au-4d states, and delocalized multi-center bonds, as well as large binding energies. The static first hyperpolarizability (?tot) is related to the cluster size and geometric structure, and the AM@GenAu (AM = Na and K) clusters exhibit the much larger ?tot values up to 13050 a.u., which are considerable to establish their strong nonlinear optical (NLO) behaviors. We hope that this study will promote further application of alkali metals-adsorbed germanium-based semiconductor materials, serving for the design of remarkable and tunable NLO materials.
Project description:Zwitterionic group 14 complexes of the alkali metals of formula [C(SiMe2OCH2CH2OMe)3M], (M-1), [Si(SiMe2OCH2CH2OMe)3M], (M-2), [Ge(SiMe2OCH2CH2OMe)3M], (M-3), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M-2 and M-3 were synthesized via reactions of [Si(SiMe2OCH2CH2OMe)4] (2) and [Ge(SiMe2OCH2CH2OMe)4] (3) with MOBu t (M = Li, Na or K), resp., in almost quantitative yields, while M-1 were prepared from deprotonation of [HC(SiMe2OCH2CH2OMe)3] (1) with LiBu t , NaCH2Ph and KCH2Ph, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCH2CH2OMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M-1-M-3, primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M-1 > M-2 > M-3. The experimental basicities and the calculated gas-phase basicities of M-1-M-3 reveal the zwitterionic alkali metal methanides M-1 to be significantly stronger bases than the analogous silanides M-2 and germanium M-3.
Project description:Exploration of new nonlinear optical (NLO) materials is of importance for infrared (IR) applications. However, it is an extremely tough challenge to design and synthesize excellent IR NLO materials with optimal performances (e.g., concurrently a large NLO response and wide bandgap). Herein, four new mixed alkali/alkaline earth metal sulfides, A2SrMIVS4 (A = Li, Na; MIV = Ge, Sn), were successfully synthesized by a motif-optimization approach using the classical AgGaS2 as a template. Note that all of them concurrently exhibit wide bandgaps (3.1-3.8 eV) and good NLO responses (0.5-0.8 × AgGaS2) with phase-matching behavior, which satisfy the balance conditions (Eg ≥ 3.0 eV and d ij ≥ 0.5 × benchmark AgGaS2) of optical performances and hence are outstanding IR NLO materials. Remarkably, both of Na2SrMIVS4 have the same structure without the structural transformation (Ge to Sn) in the reported related analogues and an interesting cation-dependent structural change is also found in Na2MIISnS4 (MII: Sr, R3c vs. Ba, I4[combining macron]2d). These results verify that the above design strategy of motif-optimization provides a feasible guide for the discovery of new IR NLO candidates and the A-AE-M-S (A = alkali metal; AE = alkaline-earth metal; M = Ga, In, Ge, Sn) system was identified as the preferred system for IR NLO materials.
Project description:Alkalides, the alkali metals in their ?1 oxidation state, represent some of the largest and most polarizable atomic species in condensed phases. This study determines the solvation environment around the sodide anion, Na?, in a system of co-solvated Li+. We present isotopically varied total neutron scattering experiments alongside empirical potential structure refinement and ab initio molecular dynamics simulations for the alkali?alkalide system, LiNa?10MeNH2. Both local coordination modes and the intermediate range liquid structure are determined, which demonstrate that distinct structural correlations between cation and anion in the liquid phase extend beyond 8.6 ?. Indeed, the local solvation around Na? is surprisingly well defined with strong solvent orientational order, in contrast to the classical description of alkalide anions not interacting with their environment. The ion-paired Li(MeNH2)4+?Na? species appears to be the dominant alkali?alkalide environment in these liquids, whereby Li+ and Na? share a MeNH2 molecule through the amine group in their primary solvation spheres.
Project description:A series of alkali metal cerium diphenylhydrazido complexes, M x (py) y [Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(iii) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(iii) oxidation state. Oxidation of the cerium(iii) diphenylhydrazido complex to the Ce(iv) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.
Project description:Structures and electronic properties of alkali metal atom-doped boron clusters MB12 0/- (M = Li, Na, K) are determined using the CALYPSO method for the global minimum search followed by density functional theory. It is found that the global minima obtained for the neutral clusters correspond to the half-sandwich structure and those of the monoanionic clusters correspond to the boat-shaped structure. The neutral MB12 (M = Li, Na, K) can be considered as a member of the half-sandwich doped B12 clusters, and the geometrical pattern of anion MB12 - (M = Li, Na, K) is a new structure that is different from other doped B12 clusters. Natural population and chemical bonding analyses reveal that the alkali metal atom-doped boron clusters MB12 - are characterized as charge transfer complexes, M+B12 2-, resulting in symmetrically distributed chemical bonds and electrostatic interactions between cationic M+ and boron atoms. The calculated spectra indicate that MB12 0/- (M = Li, Na, K) has meaningful spectral features that can be compared with future experimental data. Our work enriches the varieties of geometrical structures of doped boron clusters and can provide much insight into boron nanomaterials.
Project description:It is well known that graphite has a low capacity for Na but a high capacity for other alkali metals. The growing interest in alternative cation batteries beyond Li makes it particularly important to elucidate the origin of this behavior, which is not well understood. In examining this question, we find a quite general phenomenon: among the alkali and alkaline earth metals, Na and Mg generally have the weakest chemical binding to a given substrate, compared with the other elements in the same column of the periodic table. We demonstrate this with quantum mechanics calculations for a wide range of substrate materials (not limited to C) covering a variety of structures and chemical compositions. The phenomenon arises from the competition between trends in the ionization energy and the ion-substrate coupling, down the columns of the periodic table. Consequently, the cathodic voltage for Na and Mg is expected to be lower than those for other metals in the same column. This generality provides a basis for analyzing the binding of alkali and alkaline earth metal atoms over a broad range of systems.
Project description:The nonlinear optical (NLO) properties of meta-nitroaniline (m-NA) are evaluated via Hückel-Agrawal's approximation in a solvent environment. In this context, both the 1B and the intramolecular charge transfer (ICT) electronic transitions are considered. The benzene ring currents on the clockwise or counterclockwise direction and the corresponding Brillouin zone from 0 to ? are also considered. Besides, the Bloch equations were applied to a single cell n = 1 defined on the benzene ring. We have considered that the light beam was directed along the ring benzene bonds of m-NA; this topological hypothesis changed the crystal structure to a linear chain and the calculated optical properties were found near the experimental ones. In addition, the Fermi's golden rule was applied to the crystal state and then the calculated refraction index of m-NA had an error of less than 3% of the experimental one. On the other hand, the molar absorptivity ? of m-NA in acetonitrile for the 1B and intramolecular ICT transitions was experimentally determined to be 11?981 and 1192 L mol-1 cm-1, respectively. With this methodology, we found that the change of the charge in the NO2 group has also a strong influence on the linear and NLO properties. In addition, the dipole transition moments, which are originated from the carbon between the carbons joined to NO2 and NH2, are mainly involved in the NLO properties. Thus, the first hyperpolarizability ? z was 1.69 × 10-30 esu at ?Laser = 1064 nm, 27% of the experimental value. We attribute this difference to the evaluation of the excited dipole moment. If we attribute a separation of charge of 0.1 e in the excited state, the new dipole moment allows for the simulation of the experimental value. Besides, the calculated value of ?(3) for m-NA in a solution of acetonitrile is 2.9 × 10-13 esu at ?Laser = 1064 nm, 158% of the experimental value. The discrepancy between these values is attributed to the influence of the electronic correlation effects, that is, because of resonance structures of the aromatic ring and the zwitterionic pair of nitro and aniline. Besides, we have also evaluated the second hyperpolarizability ?, the second-order susceptibility ?(2) of m-NA and their values have similar differences to the experimental values. This type of approach is important because it reduces computing time and gives insight into the molecular causes responsible for linear and NLO properties in this type of functional groups, which can be used as building blocks in more complex polymer systems.
Project description:The organic compounds with a ?-bond system lead to electric charge delocalization which enables them to reveal fascinating nonlinear optical properties. Mono-carbonyl curcuminoids also have an appealing skeleton from the conjugation view point. Interesting chemical structures of the 3,5-bis(arylidene)-N-benzenesulfonyl-4-piperidone derivatives motivated us to perform density functional theory (DFT)-based studies. Therefore, computations using the B3LYP/6-311G(d,p) functional of DFT were executed to explore geometric parameters, highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energies, and natural bond orbital (NBO) analyses. Moreover, three different functionals such as HF, B3LYP, and M06 with the 6-311G(d,p) basis set were used to investigate the average polarizability ??? and first hyperpolarizability (?tot)-based properties of all compounds. A good concurrence among calculated and experimental parameters was obtained through root mean square error calculations. The molecular stability of piperidone derivatives was examined using the Hirshfeld surface and NBO analyses. Natural population analysis was also performed to obtain insights about atomic charges. Calculated HOMO–LUMO energies showed that charge transfer interactions take place within the molecules. Moreover, global reactivity parameters including electronegativity, chemical hardness, softness, ionization potential, and electrophilicity were calculated using the HOMO and LUMO energies. The average polarizability ??? and first hyperpolarizability (?tot) values of all compounds were observed to be larger in magnitude at the aforesaid functional than the standard compound.
Project description:New iron selenide superconductors by intercalating smaller-sized alkali metals (Li, Na) and alkaline earths using high-temperature routes have been pursued ever since the discovery of superconductivity at about 30?K in KFe?Se?, but all have failed so far. Here we demonstrate that a series of superconductors with enhanced T(c) = 30?46?K can be obtained by intercalating metals, Li, Na, Ba, Sr, Ca, Yb, and Eu in between FeSe layers by the ammonothermal method at room temperature. Analysis on their powder X-ray diffraction patterns reveals that all the main phases can be indexed based on body-centered tetragonal lattices with a?3.755-3.831 Å while c?15.99-20.54 Å. Resistivities show the corresponding sharp transitions at 45?K and 39?K for NaFe?Se? and Ba?.?Fe?Se?, respectively, confirming their bulk superconductivity. These findings provide a new starting point for studying the properties of these superconductors and an effective synthetic route for the exploration of new superconductors as well.
Project description:An accurate representation of ion solvation in aqueous solution is critical for meaningful computer simulations of a broad range of physical and biological processes. Polarizable models based on classical Drude oscillators are introduced and parametrized for a large set of monoatomic ions including cations of the alkali metals (Li(+), Na(+), K(+), Rb(+) and Cs(+)) and alkaline earth elements (Mg(2+), Ca(2+), Sr(2+) and Ba(2+)) along with Zn(2+) and halide anions (F(-), Cl(-), Br(-) and I(-)). The models are parameterized, in conjunction with the polarizable SWM4-NDP water model [Lamoureux et al., Chem. Phys. Lett. 418, 245 (2006)], to be consistent with a wide assortment of experimentally measured aqueous bulk thermodynamic properties and the energetics of small ion-water clusters. Structural and dynamic properties of the resulting ion models in aqueous solutions at infinite dilution are presented.