Excited HF Research Articles

Vibrational State-Resolved Differential Cross Sections of the F + CH4 → HF + CH3 Reaction at the Collision Energies of 3.1-13.8 kcal/mol.

We report a high-resolution crossed molecular beam experiment investigating the reaction dynamics of the F + CH4 → HF + CH3 reaction across a broad range of collision energies (3.1-13.8 kcal/mol). By using time-sliced velocity map imaging within the crossed molecular beam apparatus, we obtain correlated angular distributions and branching ratios for various product pairs (CH3(ν), HF(ν')). The resolved reactive rainbow-like features that display a distinct bulge in the angular distribution in different channels reveal the formation of vibrationally ground and excited states of the methyl radical accompanied by different rovibrationally excited HF products. These findings suggest distinct reaction dynamics for channels leading to vibrationally excited methyl radicals compared to those forming ground-state methyl radicals.

Probing the activated complex of the F + NH3 reaction via a dipole-bound state

Experimental characterization of the transition state poses a significant challenge due to its fleeting nature. Negative ion photodetachment offers a unique tool for probing transition states and their vicinity. However, this approach is usually limited to Franck-Condon regions. For example, high-lying Feshbach resonances with an excited HF stretching mode (vHF = 2-4) were recently identified in the transition-state region of the F + NH3 → HF + NH2 reaction through photo-detaching FNH3− anions, but the direct photodetachment failed to observe the lower-lying vHF = 0,1 resonances and bound states due apparently to negligible Franck-Condon factors. Indeed, these weak transitions can be resonantly enhanced via a dipole-bound state (DBS) formed between an electron and the polar FNH3 species. In this study, we unveil a series of Feshbach resonances and bound states along the F + NH3 reaction path via a DBS by combining high-resolution photoelectron spectroscopy with high-level quantum dynamical computations. This study presents an approach for probing the activated complex in a reaction by negative ion photodetachment through a DBS.

К 125-летию со дня рождения лауреата Нобелевской премии академика Николая Николаевича Семенова Цепной механизм воздействия добавок дихлордифторметана на горение водорода и метана в кислороде и воздухе

The effect of difluorodichloromethane additives on spark initiated combustion of hydrogen and methane in air and oxygen at atmospheric and reduced pressures was investigated. It has been found that the ignition concentration limit of the premixed hydrogen-air mixture in the presence of difluorodichloromethane at 1 atm exceeds 10%, while it has been shown for the first time that the ignition limit of the premixed methane-air mixture is 1% of difluorodichloromethane, which is thereby the most effective methane combustion inhibitor. This also means that the active combustion centers of hydrogen and methane, which determine the development of combustion, have a different chemical nature. Thus, the reaction including a difluorodichloromethane molecule resulting in the formation of HF (v = 2.3) during methane combustion should include a step involving the active methane combustion intermediate. Using hyperspectrometers of the visible and near-infrared ranges in the products of the oxidation reactions of hydrogen and methane in the presence of difluorodichloromethane, vibrationally excited HF molecules (v = 2.3) were first discovered. For the first time, it was found that HF molecules (v = 3) during methane combustion are formed at the moment when the maximum rate of chemical conversion is achieved, that is, reactions involving inhibitor molecules compete with the process of development of reaction chains. Keywords: chain burning, inhibition, methane, hydrogen, dichlorodifluoromethane, hyperspectrometer, high-speed color filming, radicals, excited particles.

Etching of Si3N4 by SF6/H2 and SF6/D2 plasmas

Selective plasma etching of silicon nitride (Si3N4) over silicon oxide (SiO2) is one of critical steps in the nanofabrication processes, where a direct plasma etching of Si3N4 is required for some applications. It was reported recently that Si3N4 etching by remote plasma source can be initiated by the vibrationally excited HF(v) molecules at the low concentration of atomic fluorine. Generally, the main source of HF(v) in plasma is reaction of atomic fluorine with H2 molecule. Due to this fact, the kinetic isotope effect should be observed during Si3N4 etching if replace the H2 source gas on deuterium gas (D2). The data presented here are the Si3N4 and SiO2 etching by the SF6/H2 and SF6/D2 plasmas. A different amount of H2 and D2 have been added to the SF6 discharge during the Si3N4 and SiO2 etching. It was shown that at low H2/D2 flow rate the Si3N4 etch rate is lower in the SF6/D2 discharge. This one confirms the hypothesis about Si3N4 etching by HF(v) and indicates on the fact that HF(v) gives contribution to Si3N4 etching by the direct plasma (not only by the remote plasma) at relatively high concentration of atomic fluorine.

State-to-state chemical kinetic mechanism for HF chemical lasers

State-to-state rotational relaxation processes play a critical role in predicting rotational nonequilibrium, which can significantly affect total laser power and spectral distribution. In this paper, the state-to-state rotational relaxation rate coefficients for the pumping reaction of F + H2, the rotational energy transfer processes of HF(υ, j = 0–10) + HF(υ′, j′ = 0–10) and HF(υ, j = 0–10) + H2 are calculated. Subsequently, a detailed state-to-state chemical kinetic mechanism is constructed including 61 species and 124,482 elementary reactions for HF chemical lasers. All of these rotational relaxation rate coefficients have been expressed with Arrhenius-like formulas. A comparison of the Boltzmann distribution model with the detailed state-to-state chemical mechanism has been analysed and discussed. These results show that rotational nonequilibrium processes can significantly affect the distribution of ro-vibrational excited HF molecules. The rotational distributions of HF(υ = 0–2, j) are far from equilibrium distribution. Conversely, the distributions of HF(υ = 3, 4, j) seem to be a Boltzmann distribution. These results indicate that numerical models must include the rotational nonequilibrium processes and numerical models using a Boltzmann distribution for the rotational populations cannot predict performance of real HF chemical lasers.

Emission of light charged particles and fission fragments from Hf⁎ and Pt⁎ nuclei

Using dynamical cluster-decay model, the time scale of fission and light charged particles emitted in the decay of Hf⁎ and Pt⁎ nuclei is estimated. The decay analysis is carried out for isotopes and isobars of 170,174Hf⁎ and 170,174Pt⁎ nuclei. The structural information from the excited Hf⁎ and Pt⁎ nuclei is extracted using the fragmentation potential and preformation probability, which in turn accordingly influence the cross section yields. The cross sections of evaporation residue and fission-fragments are calculated by optimizing the neck length ΔR with in the frame work of dynamical cluster-decay model (DCM). The neck length ΔR provides significant information about the shape elongation of decaying fragments and in turn provides an insight of the reaction time scale. Applying momentum conservation, the velocity and time scale of fission fragments is calculated for 170Hf⁎ nucleus at temperature T=2.011MeV, which comes out of the order of (0.7–1)×10−21 s and the same for light charged particle is 0.5×10−21 s.

Pulse energy sustainability of a burst mode closed-cycle pulsed HF chemical laser

Pulse energy sustainability of a burst mode closed-cycle pulsed HF laser is investigated with a simple theoretical model considering gas replenishment and chemical scrubbing. The effects of reactant gas consumption and de-excitation of excited HF by ground state HF are studied quantitatively. Also, experiments are carried out for comparison and validation. Simulation and experiments show that, in the burst mode operation, the energy loss caused by gas consumption is about 0.06–0.12 mJ per pulse while that induced by the de-excitation process is about 0.22–0.29 mJ per pulse, demonstrating that chemical scrubbing should play a more important role in the energy preservation of non-chain pulsed HF lasers.

Quantum dynamics of vibration-vibration energy transfer for vibrationally excited HF colliding with H2.

The rate constants for H2 -HF energy transfer processes, especially for those in vibrationally excited states, are very demanding in astrophysics and chemical laser engineering, especially for those in vibrationally excited states. Based on our recent potential energy surface, we used the coupled-states approximation including the nearest neighboring Coriolis couplings with energy-based local basis set to perform dynamics calculation for the H2 -HF energy transfer system. Rate constants for vibrational transitions (1; 3) → (0; 4), (1; 3) → (2; 2), and (0; 3) → (1; 2) were obtained. For state-to-state rate constants, transitions that have no internal angular momentum gap dominate at high temperatures. The vibrational-resolved rate constant for (1; 3) → (0; 4) initially decreases and then increases with the temperature, while those for (1; 3) → (2; 2), and (0; 3) → (1; 2) transitions monotonically increase. The calculated rate constants are in good agreement with the available experimental results. These dynamical data can be further applied to the numerical simulation of hydrogen fluoride chemical laser. © 2018 Wiley Periodicals, Inc.

The rotational excitation of HF by H

The rotational excitation of HF by H

Energetics and transition-state dynamics of the F + HOCH3 → HF + OCH3 reaction.

The F + HOCH3 → HF + OCH3 reaction is a system with 15 internal degrees of freedom that can provide a benchmark for the development of theory for increasingly complex chemical reactions. The dynamics of this reaction were studied by photoelectron-photofragment coincidence (PPC) spectroscopy carried out on the F-(HOCH3) anion, aided by a computational study of both the anion and neutral potential energy surfaces, with energies extrapolated to the CCSDT(Q)/CBS level of theory. Photodetachment at 4.80 eV accesses both the reactant and product channels for this reaction. In the product channel (HF + OCH3 + e-) of the neutral potential energy surface, vibrationally excited HF products in addition to the stable product-channel hydrogen-bonded complex (FH-OCH3) are observed in the PPC and photoelectron spectra. In addition, experimental evidence is observed for the reactant-channel van der Waals complex (F-HOCH3), in good agreement with the theoretical predictions. The relative stability of these long-lived complexes was probed by reducing the ion beam energy, increasing the product time-of-flight, indicating lifetimes on the microsecond timescale for the reactant- and product-channel complexes as well as providing evidence for long-lived vibrational Feshbach resonances associated with the HF(v > 0) + OCH3 product states. This system will provide a model for extending full-dimensionality quantum dynamics to larger numbers of degrees of freedom.

Collisional quenching of highly rotationally excited HF

Collisional excitation rate coefficients play an important role in the dynamics of energy transfer in the interstellar medium. In particular, accurate rotational excitation rates are needed to interpret microwave and infrared observations of the interstellar gas for nonlocal thermodynamic equilibrium line formation. Theoretical cross sections and rate coefficients for collisional deexcitation of rotationally excited HF in the vibrational ground state are reported. The quantum-mechanical close-coupling approach implemented in the nonreactive scattering code MOLSCAT was applied in the cross section and rate coefficient calculations on an accurate 2D HF-He potential energy surface. Estimates of rate coefficients for H and H$_2$ colliders were obtained from the HF-He collisional data with a reduced-potential scaling approach. The calculation of state-to-state rotational quenching cross sections for HF due to He with initial rotational levels up to $j=20$ were performed for kinetic energies from 10$^{-5}$ to 15000 cm$^{-1}$. State-to-state rate coefficients for temperatures between 0.1 and 3000 K are also presented. The comparison of the present results with previous work for lowly-excited rotational levels reveals significant differences. In estimating HF-H$_2$ rate coefficients, the reduced-potential method is found to be more reliable than the standard reduced-mass approach. The current state-to-state rate coefficient calculations are the most comprehensive to date for HF-He collisions. We attribute the differences between previously reported and our results to differences in the adopted interaction potential energy surfaces. The new He rate coefficients can be used in a variety of applications. The estimated H$_2$ and H collision rates can also augment the smaller datasets previously developed for H$_2$ and electrons.

Chain Reaction Mechanism in Hydrogen/Fluorine Combustion

Vibrationally excited species have been considered to play significant roles in H2/F2 reaction systems. In the present study, in order to obtain further understanding of the chain reaction mechanism in the combustion of mixtures containing H2 and F2, burning velocities for H2/F2/O2/N2 flames were measured and compared to that obtained from kinetic simulations using a detailed kinetic model, which involves the vibrationally excited species, HF(ν) and H2(ν), and the chain-branching reactions, HF(ν > 2) + F2 = HF + F + F (R1) and H2(ν = 1) + F2 = HF + H + F (R2). The results indicated that reaction R1 is not responsible for chain branching, whereas reaction R2 plays a dominant role in the chain reaction mechanism. The kinetic model reproduced the experimental burning velocities with the presumed rate constant of k2 = 6.6 × 10(-10) exp(-59 kJ mol(-1)/RT) cm(3) s(-1) for R2. The suggested chain-branching reaction was also investigated by quantum chemical calculations at the MRCI-F12+CV+Q/cc-pCVQZ-F12 level of theory.

Quasiclassical state-to-state dynamics of the F + HCl reaction on a ground 12A′ potential energy surface

Quasi-classical trajectories have been evaluated to study the state-to-state dynamic for the title reaction on a recent DHTSN PES of the ground 12A′ electronic state [Deskevich et al., J. Chem. Phys. 124 (2006) 224303]. State resolved integral and differential cross sections (DCSs), as well as product rotational polarization, have been obtained for F+HCl (v=0, j=0)→Cl+HF(v′, j′) reaction at Ecol=10.0 and 50.0kcal/mol. Both the vibrational and the rotational distributions are found to be inverted, with the peaks locating at excited final states. At Ecol=10.0kcal/mol, the vibrational resolved DCSs are mainly directed backward and correspond to a simple direct-rebound mechanism. However, for Ecol=50.0kcal/mol, the HF(v′=0) products are preferentially backward-scattered, while the vibrationally excited HF(v′=1, 2, 3) are forward- scattered. These results can be interpreted by increasing of reactive collisions with high-b, which corresponds to a “stripping” dynamics. The P(θr) and P(Φr) distributions and the polarization parameters, a1-{1}, a0{2}, are also obtained to gain insights into the chemical stereodynamics of the title reaction. The HF rotational angular momentum has been found to be both aligned and oriented, and depends sensitively on the product rotational level. Difference in polarization behavior is discussed by means of the reactive mechanism.

Quantum stereodynamics of Li + HF reactive collisions: the role of reactants polarization on the differential cross section

A complete quantum study for the state-to-state Li + HF(v,j,m) → LiF(v',j',Ω') + H reactive collisions has been performed using a wave packet method, for different initial rotational states and helicity states of the reactants. The state-to-state differential cross section has been simulated, and the polarization of products extracted. It is found that the reactivity is enhanced for nearly collinear collisions, which produces a vibrational excitation of HF, needed to overcome the late barrier. It is also found that LiF(v' = 0) products are preferentially forward scattered, while vibrationally excited LiF(v' = 1 and 2) are backward scattered. These results are interpreted with a simple reaction mechanism, based on the late character and bent geometry of the transition state, originating from a covalent/ionic crossing, which consists of two steps: the arrival at the transition state and the dissociation. In the first step, in order to get to the saddle point some HF vibrational excitation is required, which favors head-on collisions and therefore low values of m. In the second step a fast dissociation of H atom takes place, which is explained by the ionic Li(+)F(-)H character of the bent transition state: the FH(-) is repulsive making that H depart rapidly leaving a highly rotating LiF molecule. For the higher energy analyzed, where resonances slightly contribute, the orientation and alignment of product rotational states, referred to as reactants frame (with the z-axis parallel to k), are approximately constant with the scattering angle. The alignment is close to -1, showing that j' is perpendicular to k, while starting from initial states with well defined rotational orientation, as states with pure m values, the final rotational are also oriented. It is also found that when using products frame (with the z'-axis parallel to k') the rotational alignment and orientation of products varies a lot with the scattering angle just because the z' axis changes from being parallel to anti-parallel to k when varying from θ = 0 to π.

Complex angular momentum analysis of low-energy electron elastic scattering from lanthanide atoms

Electron attachment to the lanthanide and Hf atoms resulting in the formation of stable excited lanthanide and Hf anions as Regge resonances is explored in the near-threshold electron impact energy region, $E<1.0$ eV. The investigation uses the recent Regge-pole methodology wherein is embedded the electron-electron correlations together with a Thomas-Fermi--type model potential incorporating the crucial core-polarization interaction. The near-threshold electron elastic total cross sections (TCSs) for the lanthanide and Hf atoms are found to be characterized by extremely narrow resonances whose energy positions are identified with the binding energies (BEs) of the resultant anions formed during the collision as Regge resonances. The extracted BEs for excited lanthanide anions are contrasted with those of the most recently calculated electron affinities (ground state BEs). We conclude that the BEs for the ${\mathrm{Pr}}^{\ensuremath{-}}$, ${\mathrm{Tb}}^{\ensuremath{-}}$, ${\mathrm{Dy}}^{\ensuremath{-}}$, ${\mathrm{Ho}}^{\ensuremath{-}}$, ${\mathrm{Er}}^{\ensuremath{-}}$, and ${\mathrm{Tm}}^{\ensuremath{-}}$ anions of O'Malley and Beck [Phys. Rev. A 79, 012511 (2009)] are not identifiable with the electron affinities as claimed. Formation of bound excited anions is identified in the elastic TCSs of all the lanthanide atoms including Hf, except Eu and Gd. The imaginary part of the complex angular momentum $L$, $\mathrm{Im}L$ is used to distinguish between the shape resonances and the bound excited negative ions. These results challenge both experimentalists and theoreticians alike since the excited anions are very weakly bound, but mostly tenuously bound ($\mathrm{BEs}<0.1$ eV). Shape resonances and Ramsauer-Townsend minima are also presented.

Theoretical study of the dynamics of F+alkanethiol self-assembled monolayer hydrogen-abstraction reactions

The dynamics of the reactions of F atoms with octanethiol self-assembled monolayers (SAMs) has been studied using theoretical methods. F+SAM classical trajectories have been propagated directly using a quantum-mechanics (QM)/molecular-mechanics scheme in which the QM portion is described using a specific-reaction-parameters (SRP) semiempirical Hamiltonian. This SRP Hamiltonian has been derived using ab initio information of model gas-phase F+alkane reactions and its accuracy has been calibrated via comparison of the result of direct-dynamics calculations with available experiments on the F+CH(4)-->HF+CH(3) and F+C(2)H(6)-->HF+C(2)H(5) reactions. The F+SAM calculations are used to analyze HF product-energy distributions at collision energies ranging from 0.80 to 11.53 kcal mol(-1) and 0 degrees, 30 degrees, and 60 degrees incident angles with respect to the surface normal. The calculations show that while the HF product is vibrationally excited, it desorbs translationally and rotationally cold at all collision energies and incident angles explored. The calculated results shed light into recent experiments of F-atom reactions with liquid alkane surfaces by providing mechanistic understanding of the factors that govern the amount of energy deposited into the various degrees of freedom of the HF product. Specifically, examination of the dynamics of postreaction HF collisions with the surface shows the role that secondary collisions play in quenching rotational and translational excitation of HF before desorption from the surface.

Development of beam-plasma instability during the injection a low-energy electron beam into the ionospheric plasma

Results are presented from an active experiment on the injection of charged particle beams into the ionospheric plasma. The experiment was carried out in 1992 onboard the Intercosmos-25 satellite and the Magion-3 daughter satellite (APEX). A specific feature of this experiment was that both the ion and electron beams were injected upward, in the same direction along the magnetic field. The most interesting results are the excitation of HF and VLF-LF waves and the generation of fast charged particle flows, which were recorded on both satellites.

STRONG VIBRATIONAL ENHANCEMENT OF SUBSTANTIALLY ENDOTHERMIC REACTION K + HF: A TIME-DEPENDENT QUANTUM WAVE PACKET STUDY

Detailed dynamics of the substantially endothermic reaction K + HF on a new ab initio ground potential energy surface has been studied by means of time-dependent quantum wave packet calculation. The calculations showed that the reaction could be significantly enhanced by vibrational excitation of HF , but not very sensitive to initial rotational excitation. The relative and absolute integral cross sections and the logarithm of the σ(v = 1)/σ(v = 0) ratio have been calculated and compared with available experimental and theoretical results. Relatively good agreement with experiment and other calculations was obtained. Reaction rate constants of this reaction was also calculated and discussed.

Theoretical Study of the Reaction of H Atoms with Vibrationally Highly Excited HF Molecules

Vibrationally highly excited molecules react extremely fast with atoms and probably with radicals. The phenomenon can be utilized for selectively enhancing the rate of reactions of specific bonds. On the basis of quasiclassical trajectory calculations, the paper analyzes mechanistic details of a prototype reaction, H + HF(v). At vibrational quantum numbers v above 2, the reaction exhibits capture-type behavior, that is, the reactive cross section diverges as the relative translational energy of the partners decreases, both for the abstraction and for the exchange channel. The mechanism of the reaction for both channels is different at low and at high translational energy. At low vibrational energy, the reaction is activated, which is switched to capture-type at high excitation. The reason is an attractive potential that acts on the attacking H atom when the HF molecule is stretched. In contrast to the 6-SEC potential surface of Mielke et al., the switch cannot be observed on the Stark-Werner potential surface, due to a small artificial barrier at high H-HF separation, preventing the reactants from obeying the attractive potential and also proving the importance of the latter. The exchange reaction can be observed even when the total energy available for the partners is below the exchange barrier, because at low translational energies the product F atom of a successful abstraction step can re-abstract that H atom from the intermediate product H2 molecule that was originally the attacker.

Molecular elimination in photolysis of o- and p-fluorotoluene at 193 nm: Internal energy of HF determined with time-resolved Fourier transform spectroscopy

Following the photodissociation of o-fluorotoluene [o-C(6)H(4)(CH(3))F] at 193 nm, rotationally resolved emission spectra of HF(1< or =v< or =4) in the spectral region of 2800-4000 cm(-1) are detected with a step-scan Fourier transform spectrometer. HF(v< or =4) shows nearly Boltzmann-type rotational distributions corresponding to a temperature approximately 1080 K; a short extrapolation from data in the period of 0.5-4.5 mus leads to a nascent rotational temperature of 1130+/-100 K with an average rotational energy of 9+/-2 kJ mol(-1). The observed vibrational distribution of (v=1):(v=2):(v=3)=67.6: 23.2: 9.2 corresponds to a vibrational temperature of 5330+/-270 K. An average vibrational energy of 25+/-(3) (12) kJ mol(-1) is derived based on the observed population of HF(1< or =v< or =3) and estimates of the population of HF (v=0 and 4) by extrapolation. Experiments performed on p-fluorotoluene [p-C(6)H(4)(CH(3))F] yielded similar results with an average rotational energy of 9+/-2 kJ mol(-1) and vibrational energy of 26+/-(3) (12) kJ mol(-1) for HF. The observed distributions of internal energy of HF in both cases are consistent with that expected for four-center elimination. A modified impulse model taking into account geometries and displacement vectors of transition states during bond breaking predicts satisfactorily the rotational excitation of HF. An observed vibrational energy of HF produced from fluorotoluene slightly smaller than that from fluorobenzene might indicate the involvement of seven-membered-ring isomers upon photolysis.