Neutral HF Research Articles

HF Formation through Dissociative Electron Attachment-A Combined Experimental and Theoretical Study on Pentafluorothiophenol and 2-Fluorothiophenol.

In chemoradiation therapy, dissociative electron attachment (DEA) may play an important role with respect to the efficiency of the radiosensitizers used. The rational tailoring of such radiosensitizers to be more susceptive to DEA may thus offer a path to increase their efficiency. Potentially, this may be achieved by tailoring rearrangement reactions into the DEA process such that these may proceed at low incident electron energies, where DEA is most effective. Favorably altering the orbital structure of the respective molecules through substitution is another path that may be taken to promote dissociation up on electron capture. Here we present a combined experimental and theoretical study on DEA in relation to pentafluorothiophenol (PFTP) and 2-fluorothiophenol (2-FTP). We investigate the thermochemistry and dynamics of neutral HF formation through DEA as means to lower the threshold for dissociation up on electron capture to these compounds, and we explore the influence of perfluorination on their orbital structure. Fragment ion yield curves are presented, and the thermochemical thresholds for the respective DEA processes are computed as well as the minimum energy paths for HF formation up on electron capture and the underlying orbital structure of the respective molecular anions. We show that perfluorination of the aromatic ring in these compounds plays an important role in enabling HF formation by further lowering the threshold for this process and through favorable influence on the orbital structure, such that DEA is promoted. We argue that this approach may offer a path for tailoring new and efficient radiosensitizers.

Probing Orientation-Specific Charge-Dipole Interactions between Hexafluoroisopropanol and Halides: A Joint Photoelectron Spectroscopy and Theoretical Study.

The interactions between hexafluoroisopropanol (HFIP) and halogen anions X- (F-, Cl-, Br-, and I-) have been investigated using negative ion photoelectron (NIPE) spectroscopy and ab initio calculations. The measured NIPE spectrum of each [HFIP·X]- (X = Cl, Br, and I) complex shows a pattern identical to the corresponding X- by shifting to the high electron binding energy side, indicative of the formation of the [HFIP···X-] structure in which X- interacts with HFIP via charge-dipole interactions. However, the spectrum of [HFIP·F]- appears completely different from that of F- and is more similar to the spectrum of the deprotonated HFIP anion (HFIP-H-). The geometry and electron density calculations indicate that a neutral HF molecule is formed upon HFIP interacting with F- via proton transfer, rendering a stable structure of [HFIP-H···HF]-. Two conformers of [HFIP-H·HF]- with HFIP being in synperiplanar and antiperiplanar configurations, respectively, are observed, providing direct experimental evidences to show the distinctly different and orientation-specific interactions between HFIP and halide anions.

Designing defect-based qubit candidates in wide-gap binary semiconductors for solid-state quantum technologies

The development of novel quantum bits is key to extend the scope of solid-state quantum information science and technology. Using first-principles calculations, we propose that large metal ion - vacancy complexes are promising qubit candidates in two binary crystals: 4H-SiC and w-AlN. In particular, we found that the formation of neutral Hf- and Zr-vacancy complexes is energetically favorable in both solids; these defects have spin-triplet ground states, with electronic structures similar to those of the diamond NV center and the SiC di-vacancy. Interestingly, they exhibit different spin-strain coupling characteristics, and the nature of heavy metal ions may allow for easy defect implantation in desired lattice locations and ensure stability against defect diffusion. In order to support future experimental identification of the proposed defects, we report predictions of their optical zero-phonon line, zero-field splitting and hyperfine parameters. The defect design concept identified here may be generalized to other binary semiconductors to facilitate the exploration of new solid-state qubits.

Gold(I) Hydrides as Proton Acceptors in Dihydrogen Bond Formation.

Wavefunction and DFT calculations indicate that anionic dihydride complexes of AuI form strong to moderate directed Au-H⋅⋅⋅H bonds with one or two HF, H2 O and NH3 prototype proton donor molecules. The largely electrostatic interaction is influenced by relativistic effects which, however, do not increase the binding energy. Very weak Au⋅⋅⋅H associations-exhibiting a corresponding bond path-occur between neutral AuH and HF units, although ultimately F becomes the preferred donor atom in the most stable structure. Increasing the hydridicity of AuH by attachment of an electron donating NHC ligand effects Au-H⋅⋅⋅H bonding of moderate strength only with HF, whereas competing Au⋅⋅⋅H interactions dominate for H2 O and NH3 . Rare η2 coordinated and HX (X=F or OH) associated H2 complexes are produced during interaction with a single ion of stronger acidity, H2 F+ or H3 O+ . Theoretically, reaction of excess [AuH2 ]- as proton acceptor with H3 O+ or NH4+ in 3:1 or 4:1 ionic ratios, respectively, affords H⋅⋅⋅H bonded analogues of Eigen-type adducts. Outstanding analytical relationships between selected bonding parameters support the integrity of the results.

Sculpting Silica Colloids by Etching Particles with Nonuniform Compositions.

We present the synthesis of new shapes of colloidal silica particles by manipulating their chemical composition and subsequent etching. Segments of silica rods, prepared by the ammonia catalyzed hydrolysis and condensation of tetraethylorthosilicate (TEOS) from polyvinylpyrrolidone loaded water droplets, were grown under different conditions. Upon decreasing temperature, delaying ethanol addition, or increasing monomer concentration, the rate of dissolution of the silica segment subsequently formed decreased. A watery solution of NaOH (∼mM) selectively etched these segments. Further tuning the conditions resulted in rod–cone or cone–cone shapes. Deliberately modulating the composition along the particle’s length by delayed addition of (3-aminopropyl)-triethoxysilane (APTES) also allowed us to change the composition stepwise. The faster etching of this coupling agent in neutral conditions or HF afforded an even larger variety of particle morphologies while in addition changing the chemical functionality. A comparable step in composition was applied to silica spheres. Biamine functional groups used in a similar way as APTES caused a charge inversion during the growth, causing dumbbells and higher order aggregates to form. These particles etched more slowly at the neck, resulting in a biconcave silica ring sandwiched between two silica spheres, which could be separated by specifically etching the functionalized layer using HF.

Low energy electron induced reactions in fluorinated acetamide – probing negative ions and neutral stable counterparts*

Electron impact to trifluoroacetamide (CF3CONH2, TFAA) in the energy range 0–12 eV leads to a variety of negative fragment ions which are formed via dissociative electron attachment (DEA). The underlying reactions range from single bond cleavages to remarkably complex reactions that lead to loss of the neutral units HF, H2O and HNCO as deduced from their directly observed ionic counterparts (M – H2O)−, (M – HF)− and (M – HNCO)−. Also formed are the pseudo-halogen ions CN− and OCN−. All these reactions proceed dominantly via a resonance located near 1 eV, i.e., electrons at subexcitation energies trigger reactions involving multiple bond cleavages. The electron induced generation of the neutral molecules HF, H2O and HNCO in condensed TFAA films is probed by temperature controlled thermal desorption spectrometry (TDS) which can be viewed as a complementary techniques to gas-phase experiments in DEA to directly probe the neutral counterparts.

Additional Article Notification: Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis

Neutral Zr(IV) and Hf(IV) dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N'} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe₃. Their structure consists of a central ó-bonded aryl donor group (C) capable of forming robust M-C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){N⁻,C⁻,N}Me][B(C₆F₅)₄] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene-1-octene copolymerizations.

Group IV Organometallic Compounds Based on Dianionic “Pincer” Ligands: Synthesis, Characterization, and Catalytic Activity in Intramolecular Hydroamination Reactions

Neutral Zr(IV) and Hf(IV) diamido complexes stabilized by unsymmetrical dianionic N,C,N' pincer ligands have been prepared through the simplest and convenient direct metal-induced Caryl-H bond activation. Simple ligand modification has contributed to highlight the non-innocent role played by the donor atom set in the control of the cyclometallation kinetics. The as-prepared bis-amido catalysts were found to be good candidates for the intramolecular hydroamination/cyclization of primary aminoalkenes. The ability of these compounds to promote such a catalytic transformation efficiently (by providing, in some cases, fast and complete substrate conversion at room temperature) constitutes a remarkable step forward toward catalytic systems that can operate at relatively low catalyst loading and under milder reaction conditions. Kinetic studies and substrate-scope investigations, in conjunction with preliminary DFT calculations on the real systems, were used to elucidate the effects of the substrate substitution on the catalyst performance and to support the most reliable mechanistic path operative in the hydroamination reaction.

Cationic Group-IV pincer-type complexes for polymerization and hydroamination catalysis

Neutral Zr(IV) and Hf(IV) dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N'} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe3. Their structure consists of a central σ-bonded aryl donor group (C) capable of forming robust M-C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){N(-),C(-),N}Me][B(C6F5)4] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene-1-octene copolymerizations.

Molecular rearrangement reactions in the gas phase triggered by electron attachment

Bond formation and rearrangement reactions in gas phase electron attachment were studied through dissociative electron attachment (DEA) to pentafluorotoluene (PFT), pentafluoroaniline (PFA) and pentafluorophenol (PFP) in the energy range 0-14 eV. In the case of PFA and PFP, the dominant processes involve formation of [M - HF](-) through the loss of neutral HF. This fragmentation channel is most efficient at low incident electron energy and for PFP it is accompanied by a substantial conformational change of the anionic fragment. At higher energy, HF loss is also observed as well as a number of other fragmentation processes. Thermochemical threshold energies have been computed for all the observed fragments and classical trajectories of the electron attachment process were calculated to elucidate the fragmentation mechanisms. For the dominant reaction channel leading to the loss of HF from PFP, the minimum energy path was calculated using the nudged elastic band method.

Development of a Fluoride-Selective Electrode based on Scandium(III) Octaethylporphyrin in a Plasticized Polymeric Membrane

- between 10 -4.6 to 10 -1 M was observed at a glycine-phosphate buffer (pH 3.0). The selectivity pattern was observed as F - , salicylate >> SCN - > Cl - , Br - , NO3 - , ClO4 - , which is consistent with the binding constant data measur- ed in the plasticized PVC membrane based on a sandwich membrane method. This highly selective and reversible fluo- ride-sensitive electrode was employed for the analysis of hydrofluoric acid (HF). A disposable differential-type HF sen- sor was fabricated on the screen-printed electrode and demonstrated its ability to detect the neutral HF in the acidic solu- tion.

Solvent‐Dependent Dihydrogen/Dihydride Stability for [Mo(CO)(Cp*)H2(PMe3)2]+[BF4]− Determined by Multiple Solvent⋅⋅⋅Anion⋅⋅⋅Cation Non‐Covalent Interactions

Low-temperature (200 K) protonation of [Mo(CO)(Cp*)H(PMe(3))(2)] (1) by Et(2)OHBF(4) gives a different result depending on a subtle solvent change: The dihydrogen complex [Mo(CO)(Cp*)(eta(2)-H(2))(PMe(3))(2)](+) (2) is obtained in THF, whereas the tautomeric classical dihydride [Mo(CO)(Cp*)(H)(2)(PMe(3))(2)](+) (3) is the only observable product in dichloromethane. Both products were fully characterised (nu(CO) IR; (1)H, (31)P, (13)C NMR spectroscopies) at low temperature; they lose H(2) upon warming to 230 K at approximately the same rate (ca. 10(-3) s(-1)), with no detection of the non-classical form in CD(2)Cl(2), to generate [Mo(CO)(Cp*)(FBF(3))(PMe(3))(2)] (4). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X-ray crystallography as [Mo(CO)(Cp*)(FHFBF(3))(PMe(3))(2)] (5), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF(4) (-) anion through a hydrogen bond. The reason for the switch in relative stability between 2 and 3 was probed by DFT calculations based on the B3LYP and M05-2X functionals, with inclusion of anion and solvent effects by the conductor-like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non-covalent anion-solvent interactions, which modulate the anion-cation interaction ultimately altering the energetic balance between the two isomeric forms.

Enhanced Collision-Induced Decomposition Efficiency and Unraveling of Fragmentation Pathways for Anionic Adducts of Brevetoxins in Negative Ion Electrospray Mass Spectrometry

Brevetoxins are a group of natural neurotoxins characterized by polyether ring systems that are found in the blooms of red tide algae. In a conventional water/organic solvent system, without any other additives, deprotonated molecules of brevetoxins do not appear in high abundance in negative mode electrospray mass spectrometry (ES-MS) due to lack of acidic functional groups; thus, they are not well-suited for collision-induced decomposition (CID) experiments in negative mode electrospray. In this study, several anions were tested for their abilities to form anionic adducts by mixing ammonium salts of these anions with brevetoxin-2 and brevetoxin-3. Under CID, [M + Cl](-), [M + Br](-), [M + OAc](-), [M + HCOO](-), and [M + NO(3)](-) adducts all produced only the respective anions in CID experiments and thus provided no structural information. In contrast, upon CID, both [M + F](-) and [M + HCO(3)](-) precursor adducts gave structurally informative fragment peaks that exhibited similarities to those of [M - H](-) ions, which indicated that the first step in gas-phase decomposition of these anionic adducts was loss of neutral HF or H(2)CO(3) molecules, respectively, leaving deprotonated brevetoxin ([M - H](-)) to undergo consecutive fragmentations. In comparison to bicarbonate, fluoride formed adducts in higher abundance and provided more fragment peaks, thus more structural information, in MS/MS experiments. It is therefore the anion of choice to study brevetoxins in negative mode electrospray mass spectrometry using the anion attachment approach. The detailed fragmentation mechanisms are discussed, and diagnostic product ions are proposed for the brevetoxin-2 side chain (m/z 95, 133, and 151), the brevetoxin-3 side chain (m/z 97, 135, and 153), and the type-B brevetoxin backbone (m/z 725, 739, 741, and 797). To test the developed methodology, a sample of brevetoxin-2 subjected to in vitro microsomal incubation was analyzed, and a reduction product of the substrate was confirmed to have the structure of brevetoxin-3.

Structural, electronic and magnetic properties of the surfaces of tetragonal and cubic HfO2

We present ab initio density-functional theory (DFT) calculations of the structure and stability of the monoclinic (m), tetragonal (t) and cubic (c) phases of HfO2 and of the stability and the structural, electronic, and magnetic properties of the polar (001) surface of t-HfO2 and the (100) and (111) surfaces of c-HfO2. We show that on all three surfaces, a termination by Hf leads to a metallic and non-magnetic surface, while surfaces covered by a full monolayer of O are predicted to be half-metallic and ferromagnetic, the magnetisms being induced by the Coulomb repulsion between p-holes in the O-2p valence band. In contrast, the partially reduced surfaces terminated by half a monolayer of oxygen are found to be insulating and non-magnetic. Ab initio statistical mechanics in combination with the DFT total-energy calculations show that the partially reduced surfaces are stable over the entire range of admissible values of the chemical potential of oxygen. Investigations of the formation of Hf vacancies on the Hf- and O-terminated surfaces of tetragonal HfO2 demonstrate that under oxidizing conditions, the formation of Hf subsurface vacancies is energetically favored on the partially reduced O-terminated surface. The formation of Hf vacancies causes the creation of holes in the O-2p valence band and of magnetic moments on the surrounding O atoms. That the formation of near-surface Hf vacancies on the O-terminated surface is energetically favored is in contrast to a high formation energy for neutral Hf vacancies in bulk HfO2 and suggests a cooperative mechanism between surface- and vacancy-formation. We discuss our findings in relation to recent reports on ferromagnetism in ultrathin HfO2 films and other models for the formation of p-wave ferromagnetism.

Electron bound to hydrated hydrogen fluoric acids

Electron(e)-binding hydrated hydrogen fluoride clusters [e–HF(H 2O) n=1–10 ] have been studied with density functional and ab intio calculations. The hydrofluoric acid in e–HF(H 2O) n clusters is found to be undissociated at 0 K till n = 10. The e–HF(H 2O) 3 cluster is particularly unstable compared with the corresponding neutral structures, which reflects the particularly unstable antimagic number of e–water tetramer. The characteristic of “magic” numbers of electron–water clusters appears in these e–(HF)(H 2O) n clusters. The vertical detachment energies of e–HF(H 2O) n are enhanced by the HF acid as compared with those of the e-binding water clusters [e–(H 2O) n + 1 ], and the excess electron is surface bound near the terminal water molecule with two dangling hydrogen atoms. The coordination number of HF is one for n = 1–4 as a linear structure in contrast to two for n = 5–6, and three for n = 7–10. The phase transition from 2- to 3-dimensional structures appears at penta-hydrated system in contrast to hepta-hydrated system for neutral HF–water clusters. The structures for e–HF(H 2O) n=2,3 are quite different from those of the corresponding e–(H 2O) n + 1 = 3,4 , and the structures for e–HF(H 2O) n = 2–6 are quite different from those of the corresponding HF(H 2O) n = 2–6.

Cesium fluorohydrogenate, Cs(FH) 2.3F

Cs(FH) 2.3F is a liquid salt exhibiting a low viscosity of 20.1 cP and a high conductivity of 86.3 mS cm −1 at 25 °C, in spite of the relatively high melting point (16.9 °C). The high density of 2.82 g cm −3 at the liquid state is due to the heavy atomic weight and small size of cesium atom compared to the organic cations of general ionic liquids. The infrared spectroscopy indicates that this salt contains (FH) 2F − as a main anionic species. The other anionic species such as (FH) 3F − found in the cases of other M +(HF) 2.3F (M = a univalent organic cation) ionic liquid salts is not detected, suggesting its small abundance as well as the presence of neutral HF in the form of molecular and/or oligomers. The result of 1H NMR also suggests that the anions exchange HF between them. These observations coincide with the experimental result that Cs(FH) 2.3F acts as an acid against general ionic liquid fluorohydrogenates such as EMIm(FH) 2.3F (EMIm = 1-ethyl-3-methylimidazolium) to lose HF and give Cs(FH) 2F precipitate.

Effects of Base Oxide Thickness and Silicon Composition on Charge Trapping in HfSiO/SiO2 High-k Gate Stacks

This work investigates the fundamentals of charge trapping and the effects of base oxide thickness and Si composition on charge trapping in HfSiO/SiO2 high-k gate stacks using positive-bias temperature (PBT) stressing scheme. During the PBT stress, threshold voltage shift and saturation drain current degradation induced by charge trapping continue to grow and eventually become saturated, whereas the subthreshold swing and maximum transconductance remain unchanged. The extent of charge trapping increases with the decrease of base oxide thickness and Si composition in the HfSiO film, which can be explained by considering the channel-to-bulk tunneling time constant and the amount of neutral Hf–OH trapping centers in the HfSiO bulk layer. The power law dependence of saturation drain current degradation on the gate bias voltage indicates that charge trapping would become more significant if thin base oxide and low Si composition were employed in the further scaled HfSiO/SiO2 high-k gate stacks.

Characterization of Novel Nucleoside Analogs by Electrospray Ionization Mass Spectra

In this paper, we synthesized a novel nucleoside analog by coupling thymine with dimethyl dicarboxylate biphenyl (DDB). The structure of the target compound was determined using 1H nuclear magnetic resonance (NMR) and electrospray ionization tandem mass spectrometry (ESI-MS/MS). The fragmentation pathways were studied in details through ESI-MS/MS. By comparing with unsubstituted nucleosides, such as AZT, MCI, d4T and DDI, it was found that the nucleoside analog coupled with DDB would not yield the daughter ions corresponding to the fragments of the nucleoside base and arabinofuranose analogs, but would lose a neutral molecule HF and DDB easily. However, the unsubstituted nucleosides could lightly yield the fragment ions of the nucleoside base and sugar ring. Hence, electrospray ionization mass spectrometry combined with tandem mass spectrometry (MS/MS) provides a convenient method to recognize the substituted and unsubstituted nucleosides.

The bond-forming reaction between CF22+ and H2O/D2O: A computational and experimental study

Ground-state stationary points on the potential energy surface of the reaction CF22++H2O→OCF++HF+H+ were calculated using the density-functional theory hybrid method B3LYP and the ab initio coupled cluster singles and doubles with perturbative triples [CCSD(T)] algorithm. The calculations reveal a reaction mechanism involving two transition states. The first transition state involves the migration of one hydrogen within the primary collision complex and the second corresponds to the loss of a proton. The neutral HF molecular product is formed in its stable ground Σ1 state. Comparison of activation energies for the reactions of CF22+ with H2O and with D2O, calculated from Becke three parameter Lee–Yang–Parr (B3LYP) zero-point energies, slightly favor the H2O pathway by 0.04 and 0.07 eV for the first and second activations, respectively. Rate constant calculations using Rice–Ramsperger–Kassel–Marcus/quasiequilibrium theory also kinetically favor the H2O pathway in comparison with the D2O pathway. However, the magnitudes of the calculated rate constants are so large (1012–1014 s−1) that the differences between the rates of reaction of CF22+ with H2O and with D2O should not be distinguished by a crossed-beam time-of-flight mass spectrometer experiment. Indeed, the ion yields reported in this paper from new collision experiments between CF22+ and D2O showed no isotope effect when compared with previous data from collisions of CF22+ with H2O.

Hydrogen bonding and catalysis of solvolysis of 4-methoxybenzyl fluoride.

Values of k(o) = 8.0 x 10(-3) s(-1) and k(H) = 2.5 x 10(-2) M(-1) s(-1), respectively, were determined for the spontaneous and the acid-catalyzed cleavage of 4-methoxybenzyl fluoride (1-F) to form the 4-methoxybenzyl carbocation (1+). Values of k(F) = 1.8 x 10(7) M(-1) s(-1) and k(HF) = 7.2 x 10(4) M(-1) s(-1) were determined for addition of F- and HF to 1+ for reaction in the microscopic reverse direction. Evidence is presented that the reversible addition of HF to 1+ to give 1-F + H+ proceeds by a concerted reaction mechanism. The relatively small 250-fold difference between the reactivities of fluoride ion and neutral HF toward 1+ is attributed to the tendency of the strong aqueous solvation of F- to decrease its nucleophilic reactivity and to the advantage for the concerted compared with the usual stepwise pathway for addition of HF. There is no significant stabilization of the transition state for cleavage of 1-F from general acid catalysis by 0.80 M cyanoacetate buffer at pH 1.7. The estimated 3 kcal/mol larger Marcus intrinsic barrier for heterolytic cleavage of 1-F than for cleavage of 1-Cl is attributed to a lag in the development at the transition state of the ca. 30 kcal/mol greater stabilizing solvation of the product ion F- compared with Cl-. The decrease in the electronegativity of X along the series X = F, OH, Cl is accompanied by a ca. 10(10)-fold increase in the carbon basicity compared with the proton basicity of X-.