scholarly journals New Family of Ionic Supersalts with Covalent-like Directionality and Unconventional Multiferroicity

2020 ◽  
Author(s):  
Yaxin Gao ◽  
Menghao Wu ◽  
Puru Jena
Keyword(s):  
Density Functional ◽  
Building Blocks ◽  
Cluster Ions ◽  
Functional Theory ◽  
Exothermic Reactions ◽  
Ionic Bonding ◽  
New Family ◽  
Polar Materials ◽  
Switching Barriers ◽  
Covalent Nature

Abstract Ionic crystals composed of elemental ions such as NaCl are centro-symmetric and, thus, non-polar due to directionless ionic bonding interactions. To develop polar materials, the directionality feature of covalent bonding is necessary. Here, we propose a novel way where ionically bonded crystals can develop polarity by changing their building blocks from elemental ions to cluster-ions. Superalkalis and superhalogens are clusters which mimic the chemistry of alkali and halogen atoms. Equally important, unlike the elemental ions, the geometries of these superions are not spherical. Endowed with these unique features, ionic supersalts form anisotropic polar structures with ionic bonding, yet covalent-like directionality, akin to sp3 hybridized systems. Using density functional theory and extensive structure searches, we predict a series of stable supersalts, PnH4MX4 (Pn = N, P; M = B, Al, Fe; X = Cl, Br) composed of superalkali PnH4 and superhalogen MX4 ions with unprecedented properties: (1) ferroelectricity with ultra-long ion displacements (~ 3 Å); (2) ferroelasticity with ultra-large reversible strain (> 40%); and (3) both with ultra-low switching barriers (about 6 to 13 meV/atom). These values are inconceivable in traditional ferroelectric/ferroelastic materials owing to their brittle covalent nature. Coupling of ferroelectricity with ferroelasticity can further enable strain-controlled polarization as well as electrically-controlled strain. In particular, PnH4FeX4 exhibits triferroic coupling of ferroelectricity, ferroelasticity, and antiferromagnetism where the spin directions can be altered via either ferroelastic or 90-degree ferroelectric switching. These ionic supersalts can be synthesized using facile solution-processed fabrication by exothermic reactions, MPn + 4HX→PnH4MX4 or PnH4X + MX3→PnH4MX4, which may open a new chapter in multiferroics.

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

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yaxin Gao ◽  
Menghao Wu ◽  
Puru Jena
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Building Blocks ◽  
Cluster Ions ◽  
Ionic Crystals ◽  
Functional Theory ◽  
Reversible Strain ◽  
Ionic Bonding ◽  
Cluster Ion ◽  
Ferroelectric Switching

AbstractIonic 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 sp3 hybridized systems. Using density functional theory and extensive structure searches, we predict a series of stable ferroelectric/ferroelastic supersalts, PnH4MX4 (Pn = N, P; M = B, Al, Fe; X = Cl, Br) composed of superalkali PnH4 and superhalogen MX4 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, PH4FeBr4 exhibits triferroic coupling of ferroelectricity, ferroelasticity, and antiferromagnetism with controllable spin directions via either ferroelastic or 90-degree ferroelectric switching.

STRUCTURAL AND ELECTRONIC PROPERTIES OF (CnLi)+ CLUSTER IONS

2005 ◽  
Vol 16 (02) ◽  
pp. 271-280
Author(s):  
EFE YAZGAN ◽  
ŞAKIR ERKOÇ
Keyword(s):  
Density Functional Theory ◽  
Electronic Properties ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Vibrational Frequencies ◽  
Cluster Ions ◽  
Functional Theory ◽  
B3lyp Level ◽  
Structural And Electronic Properties

The structural and electronic properties of ( C n Li )+ cluster ions with n =1–6 and n =20 have been investigated by performing density functional theory calculations at B3LYP level. The vibrational frequencies of the clusters are also calculated.

Two-dimensional metal-organic frameworks Mo3(C2O)12 as promising single-atom catalysts for selective nitrogen-to-ammonia

2022 ◽  
Author(s):  
Zhen Feng ◽  
Zelin Yang ◽  
Xiaowen Meng ◽  
Fachuang Li ◽  
Zhanyong Guo ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Metal Organic Frameworks ◽  
Density Functional Theory Calculations ◽  
Reduction Reaction ◽  
Single Atom ◽  
Two Dimensional ◽  
Functional Theory ◽  
New Family ◽  
Metal Organic

The development of single-atom catalysts (SACs) for electrocatalytic nitrogen reduction reaction (NRR) remains a great challenge. Using density functional theory calculations, we design a new family of two-dimensional metal-organic frameworks...

scholarly journals Spectroscopic identification of fragment ions of DNA/RNA building blocks: the case of pyrimidine

2020 ◽  
Vol 22 (30) ◽  
pp. 17275-17290
Author(s):  
Kuntal Chatterjee ◽  
Otto Dopfer
Keyword(s):  
Density Functional Theory ◽  
Infrared Spectroscopy ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Building Blocks ◽  
Functional Theory ◽  
Fragment Ions ◽  
Sequential Loss ◽  
Spectroscopic Identification

The structure of the predominant fragments of the fundamental pyrimidine cation arising from sequential loss of HCN are identified by infrared spectroscopy of tagged ions and dispersion-corrected density functional theory calculations.

scholarly journals Microhydration of protonated biomolecular building blocks: protonated pyrimidine

2020 ◽  
Vol 22 (23) ◽  
pp. 13092-13107
Author(s):  
Kuntal Chatterjee ◽  
Otto Dopfer
Keyword(s):  
Density Functional Theory ◽  
Infrared Spectroscopy ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Building Blocks ◽  
Protonation Site ◽  
Functional Theory

The protonation site and evolution of the hydration network in microsolvated protonated pyrimidine clusters, H+Pym–(H2O)n with n = 1–4, has been explored by infrared spectroscopy and density functional theory calculations.

scholarly journals Physicochemical Insight into Coordination Systems Obtained from Copper(II) Bromoacetate and 1,10-Phenanthroline

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5324
Author(s):  
Ewelina Krejner ◽  
Tomasz Sierański ◽  
Marcin Świątkowski ◽  
Marta Bogdan ◽  
Rafał Kruszyński
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Building Blocks ◽  
Radiation Absorption ◽  
Ir Absorption ◽  
Bromoacetic Acid ◽  
Functional Theory ◽  
Hirshfeld Analysis ◽  
Coordination Systems

Two different coordination compounds of copper were synthesized from the same building blocks (1,10-phenanthroline, bromoacetate anions, and copper cations). The synthesis parameters were carefully designed and evaluated to allow the change of the resulting compounds molecular structure, i.e., formation of mononuclear (bromoacetato-O,O’)(bromoacetato-O)aqua(1,10-phenanthroline-N,N’)copper(II) and dinuclear (μ-bromido-1:2κ2)bis(μ-bromoacetato-1κO,2κO’)bis(1,10-phenanthroline-N,N’)dicopper(II) bromoacetate bromoacetic acid solvate. The crystal, molecular and supramolecular structures of the studied compounds were determined and evaluated in Hirshfeld analysis. The UV-Vis-IR absorption and thermal properties were studied and discussed. For the explicit determination of the influence of compounds structure on radiation absorption in UV-Vis range, density functional theory and time-dependent density functional theory calculations were performed.

Searching for a new family of high energy explosives by introducing N atoms, N-oxides, and NO2 into a cage adamantane

2016 ◽  
Vol 94 (8) ◽  
pp. 667-673 ◽  
Author(s):  
Dong Xiang ◽  
Hao Chen ◽  
Weihua Zhu ◽  
Heming Xiao
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Design Strategy ◽  
High Energy ◽  
Impact Sensitivity ◽  
Lower Sensitivity ◽  
Detonation Properties ◽  
Potential Candidate ◽  
Functional Theory ◽  
New Family

A design strategy that including N atoms, N-oxides, and nitro groups into a cage azaadamantane at the same time was used to design 10 polyazaoxyadamantanes (PAOAs) and eight polynitroazaoxyadamantanes (PNTAOAs). First, four stable azaadamantanes were built by replacing the tertiary C atoms of an adamantane with N atoms. Then, 10 PAOAs were designed by introducing one to four N-oxides into the four azaadamantanes. After that, eight PNTAOAs were formed when the H atoms of four N-oxide-substituted azaadamantanes were replaced with different numbers of nitro groups. Finally, their heats of formation, densities, detonation properties, and impact sensitivity were estimated by using density functional theory. Among the eight PNTAOAs, seven compounds had better detonation performances than CL-20, the outstanding, novel, high-energy, and relatively insensitive cage explosive. Two compounds had higher detonation performance and lower sensitivity than CL-20 and HMX, suggesting that their overall performances are outstanding and they may be considered as the potential candidate of high-energy explosives.

ADSORPTION REACTION OF POLAR ORGANIC MOLECULES ON ${\rm Si}^+_n$ CLUSTER IONS

2005 ◽  
Vol 19 (15n17) ◽  
pp. 2502-2507
Author(s):  
WAKANA NAKAGAWARA ◽  
HIRONORI TSUNOYAMA ◽  
ARI FURUYA ◽  
FUMINORI MISAIZU ◽  
KOICHI OHNO
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Organic Molecules ◽  
Theoretical Calculations ◽  
Cluster Ions ◽  
Silicon Cluster ◽  
Geometrical Structures ◽  
Functional Theory ◽  
Relationship Of ◽  
The Relationship

We have examined chemical reactions of small silicon cluster ions [Formula: see text] for n = 7 - 16 with polar organic molecules M ( M = CH 3 CN , CD 3 OD , C 2 H 5 CN , and C 2 H 5 OH ). The intensities of the adsorption products [Formula: see text] for m = 1 and 2 were investigated as a function of n. We found for all polar molecules that the relative intensity of Si n M + to the unreacted [Formula: see text] is smaller for n = 11, 13, and 14, that is, the adsorption reactivity is smaller for these n than others. It was also commonly observed that the [Formula: see text] ion are more intense than neighboring n. We discussed the relationship of the reactivity with the geometrical structures and the stabilities of the bare [Formula: see text] ions and adsorbed [Formula: see text] ions, from theoretical calculations based on density functional theory.

scholarly journals DFT Modelling of Tripeptides (Lysine-Tryptophan-Lysine) Interacting with Single Walled Carbon Nanotubes

2010 ◽  
Vol 7 (3) ◽  
pp. 870-874 ◽  
Author(s):  
Navaratnarajah Kuganathan
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Density Functional ◽  
Single Walled Carbon Nanotubes ◽  
Binding Energies ◽  
Functional Theory ◽  
Model Calculations ◽  
Walled Carbon Nanotubes ◽  
Dft Modelling ◽  
Covalent Nature

Model calculations are performed to predict the nature of interaction between SWNT and a tripeptide (Lys-Trp-Lys) and to calculate the binding energies and charge transfer between these two species using density functional theory. DFT calculations indicate that the interaction is of a non covalent nature. Minimal charge transfer is observed between SWNT and Lys-Trp-Lys.

Sign in / Sign up

Export Citation Format

Share Document