Quenching Cross Sections Research Articles

High-speed planar laser-induced fluorescence investigation of nitric oxide generated by hypersonic Mach reflections for computational fluid dynamics validation

In this article, the authors present an experimental investigation of the thermochemical relaxation regions downstream of symmetric Mach reflections generated in Mach 8.5 flows with stagnation enthalpies from 7 to 10 MJ/kg. The experiment was performed in the Hypervelocity Expansion Tunnel at the National Aerothermochemistry and Hypersonics Laboratory of Texas A&M University. The investigation focused on studying the nitric oxide morphology in the vicinity of a strong normal shock wave and shear layers. Experimental planar laser-induced fluorescence measurements at 250 kHz repetition rate with a quasi-simultaneous natural emission photography demonstrate a sufficient rejection of natural emission and reveal intricate flow structures in the shock vicinity. Steady computational fluid dynamics (CFD) flow solutions obtained with the US3D software were used to simulate laser-induced fluorescence signal levels for quantitative comparison against the experimentally acquired data. The investigation accomplished four objectives: complex flowfield visualization in the vicinity of the Mach stem with 4 μs temporal resolution, evaluation of the level of high-temperature chemistry effects introduced to the freestream by the expansion tunnel, both qualitative and quantitative CFD simulation validation, and cross-checking or introduction of fundamental properties of nitric oxide laser-induced fluorescence including absorption cross section for vibrationally excited states of nitric oxide and a collisional quenching cross section of nitric oxide by atomic nitrogen.

Rotational quenching of C2 with 3He and 4He collisions at ultracold temperatures

Quantum mechanical closed coupling scattering calculations are carried out at temperatures ranging from 10-8 K to 100 K for studying rotational transitions of C2 due to collisions with 3He and 4He employing our new C2-He potential energy surface computed at the CCSD(T)- F12b/aug-cc-pVQZ level of theory. Among the isotopes of He, the heavier 4He isotope has larger value of rotational quenching cross section than 3He isotope. Wigner’s threshold law holds below 10-1 cm−1. Quenching rate coefficients suggest that C2 can be cooled with 4He buffer gas. The dominance of 4He on C2 molecule is further addressed by calculating the predissociation lifetime of C2.

Collisional mixing and quenching cross sections of Cs 62P levels with methane, ethane, and propane

Mixing cross sections of Cs between the 62P1/2 and 62P3/2 levels and quenching cross sections from these levels to the ground state 62S1/2 were measured, with methane, ethane, and propane as collision partners. We excited Cs to the 6P3/2 level with a tunable nanosecond pulse laser and measured the fluorescence at the 62P1/2 level. The measured mixing cross sections with methane, ethane, and propane were (1.39 ± 0.16), (5.67 ± 0.85), and (7.91 ± 0.93)×10−15 cm2, respectively, and the statistically averaged quenching cross sections were (1.5 ± 0.25), (10 ± 2.0), and (25 ± 5.3)×10−18 cm2, respectively. The quenching cross section of Cs-propane is reported for the first time.

Vibrational quenching of CN- in collisions with He and Ar.

The vibrational quenching cross sections and corresponding low-temperature rate constants for the ν = 1 and ν = 2 states of CN-(1Σ+) colliding with He and Ar atoms have been computed ab initio using new three-dimensional potential energy surfaces. Little work has been carried out so far on low-energy vibrationally inelastic collisions for anions with neutral atoms. The cross sections and rates calculated at energies and temperatures relevant for both ion traps and astrochemical modeling are found by the present calculations to be even smaller than those of the similar C2 -/He and C2 -/Ar systems, which are in turn of the order of those existing for the collisions involving neutral diatom-atom systems. The implications of our finding in the present case mainly focus on the possible role of small computed rate constants in the dynamics of molecular cooling and the evolution of astrochemical modeling networks.

Spin exchange in scattering with polarized orthopositronium beams

We study electron and positron exchange without a spin flip in a single collision between two polarized orthopositronium beams. We use angular-momentum coupling and density-matrix techniques to calculate the probabilities of obtaining only parapositronium, both para- and orthopositronium or only orthopositronium, after the collision. The probabilities are functions of the angle between the polarization vectors of the beams and scattering amplitudes labeled with total electron spin and total positron spin. The real parts of the scattering amplitudes and products of the polarization tensors for the beams are given in terms of the probabilities for certain angles and initial spin orientations. We show that quenching probabilities for different transitions and the spin-exchange quenching cross section depend on the angle, but the ratio of the total quenching probability to the total probability for positronium scattering does not.

Ultracold rotational quenching of NCCN scattering with 3He and 4He

Rotational quenching cross sections are computed for ultracold rotational transitions of NCCN induced by collision with 3,4He. Rotational quenching of He-NCCN involving two isotopes resulted in higher cross sections for lighter isotope. Quenching cross-section in ultracold regime is found to obey Wigner’s threshold law. Rate coefficients are obtained from 10−5 to 50 K. To further analyse the isotopic effect of He, scattering lengths are computed. The imaginary part of scattering length is very large for 3He-NCCN. Rate coefficient in the limit of zero temperature is found to be an order of magnitude larger for 3He-NCCN.

Measurements of cesium mixing and quenching cross sections in methane gas: understanding sources of heating in cesium vapor lasers.

Accurate modeling of the operation of diode-pumped alkali lasers is a critical step toward the design of high-powered devices. We present precision measurements for the Cs-CH4 62P3/2 → 62P1/2 mixing cross section and the 62P3/2,1/2 → 62S1/2 quenching cross section, which are important parameters in understanding the operation and, in particular, the heat generated in a cesium vapor laser. Measurements are carried out using ultrafast laser pulse excitation and observation of fluorescence due to collisional excitation transfer in time is done using the technique of time-correlated single-photon counting. Mixing rate measurements are acquired over methane pressures of 10 - 40 Torr, resulting in a Cs-CH4 62P3/2 → 62P1/2 mixing cross section of (1.40 ± 0.08) × 10-15 cm2, while quenching rate measurements are carried out over methane pressures of 500 - 4000 Torr, resulting in a 62P3/2,1/2 → 62S1/2 quenching cross section of (1.57 ± 0.03) × 10-18 cm2. These results suggest only a slight contribution to the heating of a cesium vapor laser is due to Cs 62P quenching, contrary to previous studies. We also discuss additional possible sources of energy transfer from upper excited states of Cs.

Vibrational quenching and reactive processes of weakly bound molecular ions colliding with atoms at cold temperatures

We present a study of vibrational quenching and chemical processes of molecular ions immersed in an ultracold atomic gas by means of the quasi-classical trajectory (QCT) method. In particular, BaRb$^+(v)$ + Rb collisions are studied at cold temperatures revealing a highly efficient energy transfer between the translational degrees of freedom and internal degrees of the molecular ion. Thus leading to a large vibrational quenching cross section which follows the Langevin capture model prediction. These results play a key role on the understanding of relaxation phenomena of cold molecular ions in ultracold gases as well as in the fate of the molecules emerging trough ion-neutral-neutral three-body recombination in an cold and dense environment.

Collisional excitation transfer and quenching in Rb(5P) -methane mixtures

We have examined fine-structure mixing between the rubidium $5^{2}P_{3/2}$ and $5^{2}P_{1/2}$ states along with quenching of these states due to collisions with methane gas. Measurements are carried out using ultrafast laser pulse excitation to populate one of the Rb $5^{2}P$ states, with the fluorescence produced through collisional excitation transfer observed using time-correlated single-photon counting. Fine-structure mixing rates and quenching rates are determined by the time dependence of this fluorescence. As Rb($5^{2}P$) collisional excitation transfer is relatively fast in methane gas, measurements were performed at methane pressures of $2.5 - 25$ Torr, resulting in a collisional transfer cross section ($5^{2}P_{3/2} \rightarrow 5^{2}P_{1/2}$) of $(4.23 \pm 0.13) \times 10^{-15}$ cm$^{2}$. Quenching rates were found to be much slower and were performed over methane pressures of $50 - 4000$ Torr, resulting in a quenching cross section of $(7.52 \pm 0.10) \times 10^{-19}$ cm$^{2}$. These results represent a significant increase in precision compared to previous work, and also resolve a discrepancy in previous quenching measurements.

Diode-pumped cesium vapor laser operated with various hydrocarbon gases and compared with numerical simulation

Cesium diode pumped alkali lasers (DPALs) have been operated using various hydrocarbons (methane, ethane, and propane) and helium as a buffer gas. We find that the optimum partial pressure of hydrocarbons depends on the cross sections of the upper-state mixing reaction, while the maximum output power does not depend on the hydrocarbon species. Because the cross section of the quenching reaction between cesium and these hydrocarbons is significantly smaller than that for the upper-state mixing reaction, no direct measurement of such cross sections has been attempted to date. In this study, we attempted to determine the cross sections with the aid of DPAL simulation. Output power calculations were repeated by varying the quenching cross sections until a reasonable agreement with the experiments was met. The results indicated that the quenching cross sections of methane, ethane, and propane were 0.05 ± 0.03, 0.14 ± 0.04, and 0.23 ± 0.07 Å2, respectively. The validity of the results is supported by the fact that the cross section of methane obtained is consistent with that suggested by Yacoby et al. [Opt. Express 26, 17814 (2018)].

Experimental and theoretical studies of the Xe-OH(A/X) quenching system.

New multi-reference, global ab initio potential energy surfaces (PESs) are reported for the interaction of Xe atoms with OH radicals in their ground X2Π and excited A2Σ+ states, together with the non-adiabatic couplings between them. The 2A' excited potential features a very deep well at the collinear Xe-OH configuration whose minimum corresponds to the avoided crossing with the 1A' PES. It is therefore expected that, as with collisions of Kr + OH(A), electronic quenching will play a major role in the dynamics, competing favorably with rotational energy transfer within the 2A' state. The surfaces and couplings are used in full three-state surface-hopping trajectory calculations, including roto-electronic couplings, to calculate integral cross sections for electronic quenching and collisional removal. Experimental cross sections, measured using Zeeman quantum beat spectroscopy, are also presented here for comparison with these calculations. Unlike similar previous work on the collisions of OH(A) with Kr, the surface-hopping calculations are only able to account qualitatively for the experimentally observed electronic quenching cross sections, with those calculated being around a factor of two smaller than the experimental ones. However, the predicted total depopulation of the initial rovibrational state of OH(A) (quenching plus rotational energy transfer) agrees well with the experimental results. Possible reasons for the discrepancies are discussed in detail.

A new accurate potential energy surface for HeTiO system and rotational quenching of TiO due to He collisions

A new accurate ab initio potential energy surface (PES) of the HeTiO system is constructed. The multi-reference configuration interaction with the Davidson correction is used to obtain the energy points, and the neural network method is employed to fit the PES. State-to-state rotational quenching cross sections and rate coefficients are obtained over a wide range based on the PES. Wigner threshold law is proved to be valid in the ultralow energy regime. In comparison with 3He, 4He is more efficient for the TiO molecule cooling process in the dominant transition j = 1 → 0 due to the isotope effect.

Full-Dimensional Quantum Dynamics of SiO in Collision with H2.

We report the first full-dimensional potential energy surface (PES) and quantum mechanical close-coupling calculations for scattering of SiO due to H2. The full-dimensional interaction potential surface was computed using the explicitly correlated coupled-cluster (CCSD(T)-F12b) method and fitted using an invariant polynomial approach. Pure rotational quenching cross sections from initial states v1 = 0, j1 = 1-5 of SiO in collision with H2 are calculated for collision energies between 1.0 and 5000 cm-1. State-to-state rotational rate coefficients are calculated at temperatures between 5 and 1000 K. The rotational rate coefficients of SiO with para-H2 (p-H2) are compared with previous approximate results which were obtained using SiO-He PESs or scaled from SiO-He rate coefficients. Rovibrational state-to-state and total quenching cross sections and rate coefficients for initially excited SiO (v1 = 1, j1 = 0 and 1) in collisions with p-H2 (v2 = 0, j2 = 0) and ortho-H2 (o-H2) (v2 = 0, j2 = 1) are also obtained. The application of the current collisional rate coefficients to astrophysics is briefly discussed.

The role of near resonance electronic energy transfer on the collisional quenching of NO (A2Σ+) by C6H6 and C6F6 at low temperature

We present measurements of the collisional fluorescence quenching cross section of NO (A2Σ+) by benzene and hexafluorobenzene at a series of temperatures using a custom built slow flow cell and a pulsed de Laval nozzle test cell. The measurements show a deviation from the common harpoon mechanism of collisional fluorescence quenching, specifically the large quenching cross section of 147 Å2 at 300 K measured for benzene which is not predicted by the harpoon mechanism due to the low electron affinity of benzene (−1.5 eV). We speculate that the quenching of NO (A2Σ+) by benzene and hexafluorobenzene occurs through near resonance electronic energy transfer from the NO A-state to the A-state of the quencher via a pseudo-emission process. The predicted T−1/3 dependence of the cross section for this model is consistent with the experimental observations.

Full-dimensional quantum dynamics of rovibrationally inelastic scattering between CN and H2.

We report six-dimensional (6D) potential energy surface (PES) and rovibrational scattering calculations for the CN-H2 collision system. The PES was computed using the high-level ab initio spin-restricted coupled-cluster with single, double, and perturbative triple excitations-F12B method and fitted to an analytic function using an invariant polynomial method in 6D. Quantum close-coupling calculations are reported for rotational transitions in CN by H2 and D2 collisions in 6D as well as four-dimensional (4D) within a rigid rotor model for collision energies of 1.0-1500 cm-1. Comparisons with experimental data and previous 4D calculations are presented for CN rotational levels j1 = 4 and 11. For the first time, rovibrational quenching cross sections and rate coefficients of CN (v1 = 1,j1 = 0) in collisions with para- and ortho-H2 are also reported in full-dimension. Agreement for pure rotational transitions is found to be good, but no experimental data on rovibrational collisional quenching for CN-H2 are available. Applications of the current rotational and rovibrational rate coefficients in astrophysical modeling are briefly discussed.

Rotational quenching of CS in ultracold 3He collisions

Quantum mechanical scattering calculations of rotational quenching of CS (v=0) collision with 3He are performed at ultracold temperatures and results are compared with isotopic 4He collision. Rotational quenching cross sections and rate coefficients have been calculated in the ultracold region for rotational levels up to j=10 using the He–CS potential energy surface computed at the CCSD(T)/aug-cc-pVQZ level of theory. The quenching cross sections are found to be two orders of magnitude larger for the 3He than the 4He isotope under ultracold conditions. Wigner threshold law is found to be valid below 10−3K temperature.

Full-dimensional quantum dynamics of CO in collision with H2.

Inelastic scattering computations are presented for collisions of vibrationally and rotationally excited CO with H2 in full dimension. The computations utilize a newly developed six-dimensional potential energy surface (PES) and the previously reported four-dimensional V12 PES [P. Jankowski et al., J. Chem. Phys. 138, 084307 (2013)] and incorporate full angular-momentum coupling. At low collision energies, pure rotational excitation cross sections of CO by para-, ortho-, and normal-H2 are calculated and convolved to compare with recent measurements. Good agreement with the measured data is shown except for j1 = 0 → 1 excitation of CO for very low-energy para-H2 collisions. Rovibrational quenching results are presented for initially excited CO(v1j1) levels with v1 = 1, j1 = 1-5 and v1 = 2, j1 = 0 for collisions with para-H2 (v2 = 0, j2 = 0) and ortho-H2 (v2 = 0, j2 = 1) over the kinetic energy range 0.1-1000 cm(-1). The total quenching cross sections are found to have similar magnitudes, but increase (decrease) with j1 for collision energies above ∼300 cm(-1) (below ∼10 cm(-1)). Only minor differences are found between para- and ortho-H2 colliders for rovibrational and pure rotational transitions, except at very low collision energies. Likewise, pure rotational deexcitation of CO yields similar cross sections for the v1 = 0 and v1 = 1 vibrational levels, while rovibrational quenching from v1 = 2, j1 = 0 is a factor of ∼5 larger than that from v1 = 1, j1 = 0. Details on the PES, computed at the CCSD(T)/aug-cc-pV5Z level, and fitted with an invariant polynomial method, are also presented.

Resonant quenching of Rydberg atomic states by highly polar molecules

The results of theoretical studies of the resonant quenching and ion-pair formation processes induced by collisions of Rydberg atoms with highly polar molecules possessing small electron affinities are reported. We elaborate an approach for describing collisional dynamics of both processes and demonstrate the predominant role of resonant quenching channel of reaction for the destruction of Rydberg states by electron-attaching molecules. The approach is based on the solution of the coupled differential equations for the transition amplitudes between the ionic and Rydberg covalent terms of a quasimolecule formed during a collision of particles. It takes into account the possibility of the dipole-bound anion decay in the Coulomb field of the positive ionic core and generalizes previous models of charge-transfer processes involving Rydberg atoms to the cases, when the multistate Landau–Zener approaches become inapplicable. Our calculations for atom perturbed by , , , , , and molecules show that the curves representing the dependence of the resonant quenching cross sections on the principal quantum number n are bell-shaped with the positions of maxima being shifted towards lower values of n and the peak values, , several times higher than those for the ion-pair formation, . We obtain a simple power relation between the energy of electron affinity of a molecule and the position of maximum in n-dependence of the resonant quenching cross section. It can be used as an additional means for determining small binding energies of dipole-bound anions from the experimental data on resonant quenching of Rydberg states by highly polar molecules.

An Experimental and Theoretical Investigation of the C((1)D) + N2 → C((3)P) + N2 Quenching Reaction at Low Temperature.

The gas-phase quenching reaction C((1)D) + N2 → C((3)P) + N2 has been investigated experimentally over the temperature range 50-296 K using a supersonic flow reactor. C((1)D) atoms were produced in situ by the pulsed multiphoton dissociation of CBr4 precursor molecules. Rate constants for this process were measured using a chemical tracer method whereby the C((1)D) + H2 → CH + H reaction was employed to follow C((1)D) decays by monitoring vacuum ultraviolet laser-induced fluorescence of the atomic hydrogen product at 121.567 nm. The deactivation rates are seen to increase at lower temperature, indicating the likely influence of the CNN intermediate complex lifetime on intersystem crossing for this system. We also performed electronic structure calculations of relevant C((3)P)-N2 and C((1)D)-N2 potential energy curves as well as triplet-singlet spin-orbit coupling terms using the explicitly correlated internally contracted multireference configuration interaction method (ic-MRCI-F12). The calculations were performed for the collinear and perpendicular approach of the C atom toward the N2 molecule, which allowed us to construct the approximate spherical (isotropic) potential model of C-N2(j = 0). The computed reduced dimensional potentials were used in quantum close coupling scattering calculations of the electronic quenching cross sections and rate constants. While the calculated potential energy curves form the basis for a good qualitative description of the reaction, the calculated rate constants are significantly smaller than the measured ones, and fail to reproduce the temperature dependence of the experimental results. Several possible reasons are provided to explain the origin of these differences.

Theoretical investigation of the dynamics of O((1)D→(3)P) electronic quenching by collision with Xe.

We present the quantum close-coupling treatment of spin-orbit induced transitions between the (1)D and (3)P states of an atom in collisions with a closed-shell spherical partner. In the particular case of O colliding with Xe, we used electronic structure calculations to compute the relevant potential energy curves and spin-orbit coupling matrix elements. We then carried out quantum scattering calculations of integral and differential quenching cross sections as functions of the collision energy. The calculated differential cross sections for electronic quenching are in reasonable agreement with measurements [Garofalo et al., J. Chem. Phys. 143, 054307 (2015)]. The differential cross sections exhibit pronounced oscillations as a function of the scattering angle. By a semiclassical analysis, we show that these oscillations result from quantum mechanical interference between two classical paths.