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NASA NTRS1994

A Coupled-Cluster Study of XON (X=H, F, Cl), and the XON (left and right arrow) XNO Transition States

The XON molecules (X=H, F, and Cl) have been studied using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, CCSD(T), in conjunction with a double polarized triple-zeta basis set. The equilibrium geometries, dipole moments, harmonic vibrational frequencies and infrared intensities have been predicted. The X-O bond distance is shown to be abnormally long for X=F and Cl, and this is attributed to the degree of ionic bonding and the stability of NO(+). Based on Mulliken population analyses, it is shown that there is a significant degree of X(-), ON(+) ionic bonding character for FON and ClON, whereas for HON the ionic character is reduced and best described as H(+), NO(-). The stability of the XON molecule relative to the XNO isomer is shown to increase in the order HON<FON<ClON, although even ClON is 27.0 plus or minus 1.0 kcal/mol (0 K) less stable than ClNO. The XON (left and right arrow) XNO transition states are also investigated. FON and ClON possess the lowest barrier heights to isomerization (7.2 plus or minus 1.0 kcal/mol at 0 K), but these are sufficiently large to suggest that isomerization should not be rapid at low temperatures.

Lee, Timothy↗

DOE OSTI2019

Reversible intercalation of methyl viologen as a dicationic charge carrier in aqueous batteries

The interactions among charge carriers and electrode structures represent one of the most important considerations in the search for new energy storage devices. Currently, ionic bonding dominates the battery chemistry. In this work we report the reversible insertion of a large molecular dication, methyl viologen, into the crystal structure of an aromatic solid electrode, 3,4,9,10-perylenetetracarboxylic dianhydride. This is the largest insertion charge carrier when non-solvated ever reported for batteries; surprisingly, the kinetic properties of the (de) insertion of methyl viologen are excellent with 60% of capacity retained when the current rate is increased from 100 mA g -1 to 2000 mA g -1 . Characterization reveals that the insertion of methyl viologen causes phase transformation of the organic host, and embodies guest-host chemical bonding. First-principles density functional theory calculations suggest strong guest-host interaction beyond the pure ionic bonding, where a large extent of covalency may exist. This study extends the boundary of battery chemistry to large molecular ions as charge carriers and also highlights the electrochemical assembly of a supramolecular system.

25 ENERGY STORAGE↗

DOE OSTI2018

Comparative study of the pressure dependence of optical-phonon transverse-effective charges and linewidths in wurtzite InN

In this work, we investigate the hydrostatic pressure dependence of the zone center optical phonons of c -plane and a -plane wurtzite InN epilayers grown on GaN substrates. The longitudinal to transverse mode splitting for the A 1 and E 1 modes was found to increase with increasing pressure, whereas the associated transverse effective charge decreases for both modes as e T * ( A 1 ) = 2.93 – 9.9 × 10 - 3 P and e T * ( E 1 ) = 2.80 – 10.6 × 10 - 3 P (in units of elementary charge and P in GPa). These observations are well in line with results for other II–VI, III–V, and group-IV semiconductor compounds as far as the relation between the magnitude and sign of the pressure derivative of e T * and the bond ionicity is concerned. As the latter increases so does | ∂ e T * / ∂ P | with a sign change from positive to negative for bond ionicities around f i = 0.46 for compounds with anions belonging to the first row of the Periodic Table. A comparison of the results for InN and other nine tetrahedrally bonded compounds indicate that the pressure behavior of the transverse effective charge is mainly determined by the strength of the Pauli repulsion between cation valence electrons and those of the anion core. We also perform ab initio calculations in order to address the origin of the observed increase in linewidth of the E 2 high mode which is found to arise from a pressure-induced increase in the rate of two-phonon decay processes. In conclusion, this broadening is associated with tuning into resonance of a steep edge in the two-phonon density of states around 460 cm - 1 with the frequency of the E 2 high mode.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Making coordination networks ionic: a unique strategy to achieve solution-processable hybrid semiconductors

The development of high-performance, solution-processable semiconducting materials is crucial for the advancement of emerging clean-energy technologies such as light-emitting diodes and photovoltaics. While hybrid perovskites have shown considerable promise for implementation in these technologies, their reliance on toxic metals and relatively low stability towards moisture and chemical environments remain to be addressed. In this Chemistry Frontiers article, we describe a unique strategy to build nontoxic, robust and solution-processable hybrid semiconductors based on copper halide by incorporating ionic bonds in coordination complexes (molecular or extended network structures). Specifically, these compounds are made of anionic copper(I) halide and cationic organic ligands that form both coordinate and ionic bonds at the inorganic/organic interfaces and are referred to as all-in-one (AIO)-type structures. Here, the unique bonding nature renders the AIO-type structures with greatly enhanced solubility, excellent optical tunability and remarkable framework stability, all highly desirable for thin-film based optoelectronic devices. We will highlight the most recent progress in the development of this material group, including their design strategies, important properties and potential for clean-energy related applications. We will also briefly discuss the existing challenges and future outlook of these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Adhesion of ZrN and Al 2 O 3 coatings on U metal from first-principles

To understand the role of alumina layer in the adhesion of ZrN coating on U-Mo surface using atomic layer deposition (ALD) technique, we investigate the interfaces of ZrN/U, Al 2 O 3 /U, and ZrN/Al 2 O 3 using first-principles density-functional theory calculations. The preferred interfacial plane orientation relationships and terminations for all the interfaces are predicted. Calculations show that both lattice mismatch and interfacial bonding play crucial roles in determining the adhesion strength of ZrN and Al 2 O 3 coatings on U metal surface. The strength of Al 2 O 3 /U and ZrN/Al 2 O 3 interfaces are found to be substantially higher than that of ZrN/U interface. The strong interfacial adhesion of Al 2 O 3 /U and ZrN/Al 2 O 3 interfaces is ascribed to the formation of ionic bonds at the interface, as compared to weak metallic bonds formed in ZrN/U interface. Furthermore, the formation of metal-oxygen ionic bonds at interface explains the role of alumina layer in the improved adhesion of ZrN coating on U-Mo surface.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Investigation of the role of hydrogen bonding in ionic liquid-like salts with both N- and S-soft donors

In search of ionic liquids (ILs) with multiple types of soft donor atoms capable of preferentially complexing a range of soft metal ions over harder ions, we investigated structural clues to the role of hydrogen bonding in IL behavior through a series of salts with anions containing both N- and S-donor atoms based on azole thiolates. Reaction of equimolar amounts of triethylamine (Et 3 N) or diisobutylamine (DBA) with 1-phenyl-1H-tetrazole-5-thiol (PhTzSH), 1-methyl-1H-tetrazole-5-thiol (MeTzSH), or 5-methyl-1,3,4-dithiazole-2-thiol (MeDiTSH) yielded [Et 3 NH][MeTzS] (1), a yellow liquid, and the low melting yellow solids [DBAH][MeTzS] (2), [Et 3 NH][PhTzS] (3), [DBAH][PhTzS] (4), [Et 3 NH][MeDiTS] (5), and [DBAH][MeDiTS] (6). Thermal analysis revealed that all of them qualify as ILs with melting points below 100 °C. Single crystal X-ray structure analysis of 2–6 revealed the presence of an extensive H-bonding network that includes the rare N–H$\cdots$S hydrogen bonds in 3, 4, and 6. These weaker interactions appear to significantly influence thermal behavior, where strong bonding leads to higher melting temperatures and lower decomposition points.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

A family of ionic supersalts with covalent-like directionality and unconventional multiferroicity

Ionic crystals composed of elemental ions such as NaCl are non-polar due to directionless ionic bonding interactions. Here, we show that these can develop polarity by changing their building blocks from elemental ions to superalkali and superhalogen cluster-ions, which mimic the chemistry of alkali and halogen atoms, respectively. Due to the non-spherical geometries of these cluster ions, corresponding supersalts form anisotropic polar structures with ionic bonding, yet covalent-like directionality, akin to sp 3 hybridized systems. Using density functional theory and extensive structure searches, we predict a series of stable ferroelectric/ferroelastic supersalts, PnH 4 MX 4 (Pn = N, P; M = B, Al, Fe; X = Cl, Br) composed of superalkali PnH 4 and superhalogen MX 4 ions. Unlike traditional ferroelectric/ferroelastic materials, the cluster-ion based supersalts possess ultra-low switching barrier and can endure large ion displacements and reversible strain. In particular, PH 4 FeBr 4 exhibits triferroic coupling of ferroelectricity, ferroelasticity, and antiferromagnetism with controllable spin directions via either ferroelastic or 90-degree ferroelectric switching.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Pt-Assisted Carbon Remediation of Mo2C Materials for CO Disproportionation

Using the CO disproportionation (Boudouard) reaction as a probe reaction, an in-depth analysis of temperature-programmed pulse response data shows that the addition of Pt to Mo2C mitigates deactivation of Mo active sites by acting as a carbon collector. CO2 production on Mo2C and Pt/Mo2C materials is dependent on both the activation energy and the CO surface concentration. Detailed plane-wave density functional theory calculations of the CO adsorption and disproportion reactions on Mo2C-supported Pt nanoparticles (NPs) are reported. The Mo2C was modeled by the ß-Mo2C (100) surface, and the Pt/Mo2C interface was modeled by the addition of 12 Pt atoms to the Mo2C (100) surface (12Pt@Mo2C). The potential energy surfaces of the Boudouard reaction were calculated on pure Mo2C, 12Pt@Mo2C, and Pt (111) surfaces. CO dissociation readily occurs on the Mo2C (100) surface, but not on the Pt (111) surface, with the former being exothermic and the latter being endothermic. At the Pt/Mo2C interface, CO dissociation is still exothermic, but with a larger energy barrier. The Boudouard reaction takes place on the Mo2C region, where CO2 is formed from a surface O atom dissociated from one CO molecule in reaction with another CO molecule, leaving one C atom on the surface. C adsorption is preferential on the Pt site in comparison to the Mo site. The supported Pt domains can collect the remaining C atoms, facilitating further CO2 formation on the active Mo sites. A Bader charge analysis shows that the surface metal-carbon bond is a mixture of covalent and ionic bonds, whereas the surface metal-oxygen bond is ionic. Electron localization function (ELF) and partial charge density calculations agree well with the Bader charge analysis. These computational results are consistent with experimental observations of the interaction of CO with Mo2C nanotube supported Pt domains in the transient regime under far from equilibrium conditions. The Boudouard reaction is an important side reaction, and the unexpected role found for Pt as a carbon collector, with Mo serving as a disproportionation site, provides a unique vantage point for understanding carbon and coke formation on catalytic materials.

Pt-assisted carbon remediation, Pt/Mo2C interface,↗

DOE OSTI2026

Modulating the Lattice Stability in Sodium-Layered Oxide Cathodes through Inductive Effect

Stability and safety of sodium layered oxide cathodes relative to lithium analogs remain a critical concern, yet its fundamental origin remains poorly understood. Here, we examine the role of sodium – oxygen bond ionicity in governing outgassing by introducing 5% lithium (Li), potassium (K), or both into layered NaNiO 2 (NNO), yielding Na 0.95 Li 0.05 NiO 2 , Na 0.95 K 0.05 NiO 2 , and Na 0.90 Li 0.05 K 0.05 NiO 2 . Online electrochemical mass spectrometry at 4.3 V reveals that K substitution increases gas evolution with similar charge capacity, whereas Li substitution reduces gas evolution by nearly 80% with only a 16% capacity decrease. Capacity-controlled experiments show that NNO must be charged to only 3.8 V (144 mA h g -1 ) to achieve gas evolution comparable to Na 0.95 Li 0.05 NiO 2 charged to 4.3 V (175 mA h g -1 ). These results demonstrate that tuning alkali-metal–oxygen bond ionicity through the inductive effect regulates Ni–O covalency, lattice oxygen stability, and interfacial reactivity, providing design guidance for safer sodium layered oxide cathodes.

25 ENERGY STORAGE↗

DOE OSTI2023

Satellite-Dominated Sulfur L 2,3 X-ray Emission of Alkaline Earth Metal Sulfides

The sulfur L 2,3 X-ray emission spectra of the alkaline earth metal sulfides BeS, MgS, CaS, SrS, and BaS are investigated and compared with spectra calculations based on density functional theory. Very distinct spectral shapes are found for the different compounds. With decreasing electronegativity of the cation, that is, increasing ionic bonding character, the upper valence band width and its relative spectral intensity decrease. These general trends are qualitatively reproduced by the spectra calculations, which give quite an accurate description of the spectral shapes in the upper valence band region. On the low energy side of the sulfur 3s → 2p transition dominating the spectra, we find strong satellites caused by "semi-Auger" decays involving configuration interaction. These satellites, previously believed to be energetically forbidden for sulfur L 2,3 emission and only observed for the L 2,3 emission of Cl to Cr, increase in intensity as the bonding character becomes more ionic and dominate the spectra for SrS and BaS. The intensities, energies, and widths of the satellites vary strongly between the investigated compounds, giving a very specific spectral fingerprint that can be used for speciation analysis.

36 MATERIALS SCIENCE↗

DOE OSTI2022

A -type antiferromagnetic order in the Zintl-phase insulator EuZn 2 P 2

Zintl phases, containing strongly covalently bonded frameworks with separate ionically bonded ions, have emerged as a critical materials family in which to couple magnetism and strong spin-orbit coupling to drive diverse topological phases of matter. Here we report the single-crystal synthesis, magnetic, thermodynamic, transport, and theoretical properties of the Zintl compound EuZn 2 P 2 that crystallizes in the anti-La 2 O 3 (CaAl 2 Si 2 ) P-3m1 structure, containing triangular layers of Eu 2+ ions. In-plane resistivity measurements reveal insulating behavior with an estimated activation energy of E g = 0.11eV. Specific heat and magnetization measurements indicate antiferromagnetic ordering at T N = 23K. Curie-Weiss analysis of in-plane and out of plane magnetic susceptibility from T = 150 to 300 K yields p eff = 8.61 for μ 0 H⊥c and p eff = 7.74 for μ 0 H//c, close to the expected values for the 4f 7 J = S = 7/2 Eu 2+ ion and indicative of weak anisotropy. Below T N , a significant anisotropy of χ ⊥ /χ // ≈ 2.3 develops, consistent with A-type magnetic order as observed in isostructural analogs and as predicted by the density functional theory calculations reported herein. The positive Weiss temperatures of θ W =19.2K for μ 0 H⊥c and θ W =41.9K for μ 0 H//c show a similar anisotropy and suggest competing ferromagnetic and antiferromagnetic interactions. Comparing Eu magnetic ordering temperatures across trigonal EuM 2 X 2 (M= divalent metal, X= pnictide) shows that EuZn 2 P 2 exhibits the highest ordering temperature, with variations in T N correlating with changes in expected dipolar interaction strengths within and between layers and independent of the magnitude of electrical conductivity. These results provide experimental validation of the crystochemical intuition that the cation Eu 2+ layers and the anionic (M 2 X 2 ) 2– framework can be treated as electronically distinct subunits, enabling further predictive materials design.

36 MATERIALS SCIENCE↗

DOE OSTI2019

Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo

We here develop a fully quantum embedded version of initiator full configuration interaction quantum Monte Carlo (i–FCIQMC) and apply it to study an ionic bond (lithium hydride, LiH) and a covalent bond (hydrogen flouride, HF) physisorbed to a benzene molecule. The embedding is performed using a recently developed Huzinaga projection operator approach, which affords good synergy with i–FCIQMC by minimizing the number of orbitals in the calculation. When considering the dissociation energy of these bonds into closed-shell ionic fragments, we find that i–FCIQMC embedded in density functional theory (i–FCIQMC-in-DFT) delivers comparable accuracy with coupled cluster singles and doubles with perturbative triples embedded in density functional theory (CCSD(T)-in-DFT). In treating the bond dissociation energy curve of HF, i–FCIQMC-in-DFT has improved accuracy over CCSD(T)-in-DFT due to the presence of strong correlation. Lastly, we discuss the implications of the new i–FCIQMC-in-DFT method as applied to bond breaking in catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Facing the Challenges of Borderline Oxidation State Assignments Using State-of-the-Art Computational Methods.

The oxidation state (OS) of metals and ligands in inorganic complexes may be defined by carefully curated rules, such as from IUPAC, or by computational procedures such as the effective oxidation state (EOS) or localized orbital bonding analysis (LOBA). Such definitions typically agree for systems with simple ionic bonding and innocent ligands but may disagree as the boundary between ionic and covalent bonds is approached, or as the role of ligand noninnocence becomes nontrivial, or high oxidation states of metals are supported by heavy dative bonding, and so on. This work systematically compares IUPAC, EOS, and LOBA across a series of complexes where OS assignment is challenging. These systems include high-valent transition metal oxides, transition metal complexes with noninnocent ligands such as dithiolate and nitrosyl, metal sulfur dioxide adducts, and two transition metal carbene complexes. The differences in OS assignment by the three methods are carefully discussed, demonstrating the synergy between EOS and LOBA. In addition, a clarity index for LOBA OS assignments is introduced that provides an indication of whether or not its predictions are close to the ionic-covalent boundary.

Gimferrer, Martí↗

DOE OSTI2017

Tandem Aromatization of Oxygenated Furans by Framework Zinc In Zeolites. A Computational Study

We have performed electronic structure calculations to characterize the active site of the zeolite CIT-6 (isomorphically substituted Zn-Beta) and to study the Diels–Alder dehydrative aromatization of methyl-5-(methoxymethyl)-furoate (MMFC) and of the dimethyl ester of 2,5-furan-dicarboxylic acid (DMFDC) with ethylene. Three types of active sites have been investigated: a site where the framework charge was balanced by two protons (Z0); a site with an H + and a Li + as counter-cations (Z 1 ); and an active site with two Li + counter-cations (Z 2 ). Using NBO and Bader analysis, we conclude that Zn incorporation into the zeolite framework is not through covalent bonding to framework oxygen atoms but rather is through ionic bonding. Despite the ionic character of the active site and the generally strong Lewis acidic nature of Zn(II) cations, we find no catalysis of the Diels–Alder reaction for the two furans tested. On the other hand, the dehydration of the Diels–Alder cycloadduct can be either Brønsted or Lewis acid catalyzed depending on the active site type. The Z 0 -type sites are found to be more active than the Z 1 - and Z 2 -type sites. Furthermore, the Z 0 -type sites exhibit both Lewis and Brønsted acid characters with similar catalytic activities. In full agreement with experiment, we find that the conversion of MMFC to (4-methoxymethyl) benzenecarboxylate via Diels–Alder dehydrative aromatization is easier than the conversion of DMFDC to dimethyl terephthalate as the two electron withdrawing groups in DMFDC stabilize the corresponding cycloadduct against dehydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Bioderived fuels and methods of making the same

The present disclosure relates to a composition that includes a first oxide having a phosphate, a ratio of Brønsted acid sites to Lewis acid sites between 0.05 and 1.00, and a total acidity between 50 μmol/g and 300 μmol/g, where the phosphate is at least one of a functional group covalently bonded to the first oxide and/or an anion ionically bonded to the first oxide.

Hafenstine, Glenn Richard↗

DOE OSTI2023

Bioderived fuels and methods of making the same

Hafenstine, Glenn Richard↗

DOE OSTI2017

Descriptors for thermal expansion in solids

Thermal expansion in materials can be accurately modeled with careful anharmonic phonon calculations within density functional theory. However, because of interest in controlling thermal expansion and the time consumed evaluating thermal expansion properties of candidate materials, either theoretically or experimentally, an approach to rapidly identifying materials with desirable thermal expansion properties would be of great utility. When the ionic bonding is important in a material, we show that the fraction of crystal volume occupied by ions, (based upon ionic radii), the mean bond coordination, and the deviation of bond coordination are descriptors that correlate with the room-temperature coefficient of thermal expansion for these materials found in widely accessible databases. Correlation is greatly improved by combining these descriptors in a multi-dimensional fit. This fit reinforces the physical interpretation that open space combined with low mean coordination and a variety of local bond coordinations leads to materials with lower coefficients of thermal expansion, materials with single-valued local coordination and less open space have the highest coefficients of thermal expansion.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Eco-friendly, solution-processable and efficient low-energy lighting phosphors: copper halide based hybrid semiconductors Cu 4 X 6 (L) 2 (X = Br, I) composed of covalent, ionic and coordinate bonds

A series of copper halide based inorganic–organic hybrid semiconductors have been synthesized. Structural analysis confirms that all compounds are composed of one-dimensional Cu 4 X 6 2- anionic chains that coordinate to cationic ligands via Cu–N dative bonds. Different coordination affinities of the ligands lead to two types of ligand arrangements with various structural distortions. All compounds are highly resistant to heat and moisture as a result of the combination of coordinate and ionic bonds. Low energy emission with high efficiency is achieved for these compounds and the emission energy (~552–615 nm) and color (yellow-orange) can be tuned by varying the ligand and halogen element. The electronic structure and luminescence mechanism are examined by both experimental and theoretical methods. More importantly, all compounds demonstrate good solubility in polar aprotic solvents, a desired property that is absent in all other CuX hybrid families of extended structures, which is attributed primarily to the ionic nature of this material class. Furthermore, the good solution-processability, and cost effective and easily scalable synthesis coupled with high quantum efficiencies and framework stability make these hybrid materials promising phosphors for general lighting applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗