Burst-mode velocimetry of hypersonic flow by nitric oxide ionization induced flow tagging and imaging.

This Letter describes, to the best of our knowledge, a new approach to flow tagging, nitric oxide (NO) Ionization Induced Flow Tagging and Imaging (NiiFTI), and presents the first experimental demonstration for single-shot velocimetry in a near Mach 6 hypersonic flow at 250 kHz. The mean velocity of 860 m/s was measured with a single-shot standard deviation of as low as 3.4 m/s and mean velocity uncertainty of 5.5 m/s. NiiFTI is characterized by a long fluorescence lifetime of nitrogen with 1e decay of approximately 50 µs measured in air. The method relies on a single nanosecond laser combined with a high-speed camera, creating an opportunity for the utilization of a typical nitric oxide (NO) laser-induced fluorescence (LIF) experimental setup with minor modifications as well as pulse-burst lasers (PBLs) for ultrahigh repetition rates.

Rotational Distributions and Imaging of Singlet O2 Following Spin-Forbidden Photodissociation of O3.

We report REMPI spectra and velocity-mapped ion images of the O2(a1Δg) and (b1Σg+) fragments arising from the spin-forbidden photodissociation of O3 near 320 and 330 nm. The O2(a1Δg, v = 0) REMPI spectrum following a 320 nm dissociation shows enhanced peak intensity for the odd rotational states relative to the even states, which is the opposite of the trend observed by Gunthardt et al. ( J. Chem. Phys. 2019, 151, 224302) for spin-allowed dissociation at 266 nm but is consistent with the couplings between the B state and 3A' and 3A″ states calculated by Grebenshchikov and Rosenwaks ( J. Phys. Chem. A 2010, 114, 9809-9819). There are no significant differences between the ion image angular distributions of fragments in odd and even rotational states, which indicates a cold distribution of O3 and supports the explanation that the alternation in peak intensities results from a difference in the couplings. Quantitative analysis of the image angular distributions was limited due to the single laser polarization geometry accessible in one-color experiments. Radial distributions of the 320 nm images indicate a broad rotational distribution, evidenced in bimodal speed distributions with peaks corresponding to both high (j = 35-43) and low (j = 17-20) rotational states. The REMPI spectrum of O2(a1Δg) near 330 nm was collected, and while quantitative population analysis is difficult because of the perturbed resonant state, the spectrum clearly supports a broad rotational distribution as well, consistent with the images collected at 320 nm. A 2D-REMPI spectrum was collected following dissociation of O3 near 330 nm, which showed evidence of contributions from O2 fragments in both the a1Δg and b1Σg+ states. The rotational distribution for the O2(b1Σg+, v = 0) product peaks at j = 32 and is narrower than that of the O2(a1Δg) fragment, consistent with distributions reported by O'Keeffe et al. at longer dissociation wavelengths ( J. Chem. Phys. 2002, 117, 8705-8709). At smaller radii in the 2D-REMPI spectrum, there is additional signal assigned to v = 1-4 of O2(b1Σg+), with rotational distributions similar to v = 0. The vibrational distribution of the O2(b1Σg+) fragment peaks at v = 0, with populations monotonically decreasing with increasing vibrational state. Ion image angular distributions of the O2(b1Σg+) fragment and the corresponding anisotropy parameters are also reported.

Ozone Photodissociation in the Singlet Channel at 226 nm.

We report the rotational state distribution and vector correlations of the O2(a 1Δg, v = 0) fragments arising from the 226 nm photodissociation of jet-cooled O3. Consistent with previously reported trends, the rotational distribution is shifted to higher rotational states with decreasing wavelength. We observe highly suppressed odd rotational state populations due to a strong Λ-doublet propensity. The measured rotational distribution is in agreement with classical trajectory calculations for the v = 0 products, although the distribution is slightly narrower than predicted. The spatial anisotropy follows the previously observed trend of decreasing ß with increasing photon energy with ß = 0.72 ± 0.14 for v = 0, j = 38. As expected for a triatomic molecule, the v-j correlation is consistent with v perpendicular to j, but the measured correlation is nonlimiting due, in part, to rotational and translational depolarization. The j-dependent line width of the O2(a 1Δg) REMPI spectrum is also discussed in connection with the lifetime of the resonant O2(d 1Πg) state due to predissociation via the II 1Πg valence state.

Dynamics and vector correlations of vacuum ultraviolet (VUV) photodissociation of CO2 at 155 nm.

In this work, the CO2 Vacuum Ultraviolet (VUV) photodissociation dynamics of the dominant O(1D) channel near 155 nm have been studied using Velocity Map Imaging (VMI) technique. Correlations among the transition dipole moment of the parent molecule, recoil velocity vector and rotational angular momentum vector of the photofragments were extracted from the anisotropic angular distributions of the images. The vector correlations extracted indicated a picture of photodissociation mainly via the excited 21A' (A) state. The transition dipole moment  lies in the bending molecular plane, and the j⃑ is pointing perpendicular to the plane, while the µ-v vectors angle is between 41°-45°. In addition, a clear trend was observed. As the product CO rotational state j increases, the spatial anisotropy parameter (ß ≡ 2ß20(20)) decreases. This j-dependent attenuation of spatial anisotropy parameter can be explained mainly with the consideration of non-axial recoil effect. These results are in good agreement with both theoretical work and previous experimental work.

Comparison of intermolecular energy transfer from vibrationally excited benzene in mixed nitrogen-benzene baths at 140 K and 300 K.

Gas phase intermolecular energy transfer (IET) is a fundamental component of accurately explaining the behavior of gas phase systems in which the internal energy of particular modes of molecules is greatly out of equilibrium. In this work, chemical dynamics simulations of mixed benzene/N2 baths with one highly vibrationally excited benzene molecule (Bz*) are compared to experimental results at 140 K. Two mixed bath models are considered. In one, the bath consists of 190 N2 and 10 Bz, whereas in the other bath, 396 N2 and 4 Bz are utilized. The results are compared to results from 300 K simulations and experiments, revealing that Bz*-Bz vibration-vibration IET efficiency increased at low temperatures consistent with longer lived "chattering" collisions at lower temperatures. In the simulations, at the Bz* excitation energy of 150 kcal/mol, the averaged energy transferred per collision, ⟨ΔEc⟩, for Bz*-Bz collisions is found to be ∼2.4 times larger in 140 K than in 300 K bath, whereas this value is ∼1.3 times lower for Bz*-N2 collisions. The overall ⟨ΔEc⟩, for all collisions, is found to be almost two times larger at 140 K compared to the one obtained from the 300 K bath. Such an enhancement of IET efficiency at 140 K is qualitatively consistent with the experimental observation. However, the possible reasons for not attaining a quantitative agreement are discussed. These results imply that the bath temperature and molecular composition as well as the magnitude of vibrational energy of a highly vibrationally excited molecule can shift the overall timescale of rethermalization.

Origin of the "odd" behavior in the ultraviolet photochemistry of ozone.

The origin of the even-odd rotational state population alternation in the 16O2(a1Δg) fragments resulting from the ultraviolet (UV) photodissociation of 16O3, a phenomenon first observed over 30 years ago, has been elucidated using full quantum theory. The calculated 16O2(a1Δg) rotational state distribution following the 266-nm photolysis of 60 K ozone shows a strong even-odd propensity, in excellent agreement with the new experimental rotational state distribution measured under the same conditions. Theory indicates that the even rotational states are significantly more populated than the adjacent odd rotational states because of a preference for the formation of the A' Λ-doublet, which can only occupy even rotational states due to the exchange symmetry of the two bosonic 16O nuclei, and thus not as a result of parity-selective curve crossing as previously proposed. For nonrotating ozone, its dissociation on the excited B1A' state dictates that only A' Λ-doublets are populated, due to symmetry conservation. This selection rule is relaxed for rotating parent molecules, but a preference still persists for A' Λ-doublets. The A''/A' ratio increases with increasing ozone rotational quantum number, and thus with increasing temperature, explaining the previously observed temperature dependence of the even-odd population alternation. In light of these results, it is concluded that the previously proposed parity-selective curve-crossing mechanism cannot be a source of heavy isotopic enrichment in the atmosphere.

Evidence for lambda doublet propensity in the UV photodissociation of ozone.

The photodissociation of O3 at 266 nm has been studied using velocity mapped ion imaging. We report temperature-dependent vector correlations for the O2(a1Δg, v = 0, j = 18-20) fragments at molecular beam temperatures of 70 K, 115 K, and 170 K. Both the fragment spatial anisotropy and the v-j correlations are found to be increasingly depolarized with increasing beam temperature. At all temperatures, the v-j correlations for the j = 19 state were shown to be reduced compared to those of j = 18 and 20, while no such odd/even rotational state difference was observed for the spatial anisotropy, consistent with previous measurements. We find that temperature-dependent differences in the populations and v-j correlations between the odd and even rotational states can be explained by a Λ-doublet propensity model. Although symmetry conservation should lead to formation of only the A' Λ-doublet component, and only even rotational states, out-of-plane rotation of the parent molecule breaks the planar symmetry and permits the formation of the A″ Λ-doublet component and odd rotational states. A simple classical model to treat the effect of parent rotation on the v-j correlation and the odd/even rotational population alternation reproduces both the current measurements and previously reported rotational distributions, suggesting that the "odd" behavior originates from a Λ-doublet propensity, and not from a mass independent curve crossing effect, as previously proposed.

Temperature perturbation related to the invisible ink vibrationally excited nitric oxide monitoring (VENOM) technique: a simulation study.

The limits of applicability of the invisible ink variant of the vibrationally excited nitric oxide monitoring (VENOM) technique for three distinct flow fields is reported in this work. This technique involves the generation of a grid of vibrationally excited NO (X,Π2) by exciting the NO A-X electronic transition at 226 nm, which subsequently relaxes via fluorescence and collisional quenching to produce vibrationally excited NO (X,Π2). This grid is then probed by two laser sheets tuned to distinct rotational states. The resulting images allow for the simultaneous measurement of temperature and velocity. The flow fields presented in this work provide a range of NO concentrations, vibrational lifetimes, pressures, temperatures, and collisional quenching, which explore the applicability of the invisible ink variant to a wide range of conditions. We have modelled the initial NO, O2, and N2 vibrational and rotational energy distribution resulting from the combination of fluorescence and quenching of electronically excited NO. The subsequent rethermalization of the sample, in particular the long-time vibrational relaxation, has been modelled using a forced harmonic oscillator model. The time-dependent temperature perturbation due to the invisible ink technique is evaluated for two distinct timescales: a short-timescale temperature rise resulting from collisional quenching and rotational/translational thermalization and a long-timescale temperature rise caused by vibrational thermalization. Under low pressures where fluorescence dominates quenching, there is minimal temperature perturbation of the flow field on the timescale of a VENOM measurement, and the short-timescale temperature perturbation only becomes significant at high NO seed concentrations. The predicted signal-to-noise ratio of the invisible ink method is unaffected for low-pressure, low-temperature flow fields. However, preserving signal-to-noise ratio for a high-temperature, high-pressure flow field could prove challenging due to the impact of quenching and self-absorption. Overall, we find that the invisible ink method is predicted to be a viable laser-based diagnostic for velocimetry and thermometry over a wide range of experimental conditions.

Nascent O2 (a 1Δg, v = 0, 1) rotational distributions from the photodissociation of jet-cooled O3 in the Hartley band.

We report rotational distributions for the O2 (a 1Δg) fragment from the photodissociation of jet-cooled O3 at 248, 266, and 282 nm. The rotational distributions show a population alternation that favors the even states, as previously reported for a 300 K sample by Valentini et al. [J. Chem. Phys. 86, 6745 (1987)]. The alternation from the jet-cooled precursor is much stronger than that observed by Valentini et al. and in contrast to their observations does not depend strongly on the O2 (a 1Δg) vibrational state or photolysis wavelength. The odd/even alternation diminishes substantially when the ozone beam temperature is increased from 60 to 200 K, confirming its dependence on parent internal energy. The magnitude of the even/odd alternation in product rotational states from the cold ozone sample, its temperature dependence, and other experimental and theoretical evidence reported since 1987 suggest that the alternation originates from a Λ-doublet propensity and not from a mass independent curve crossing effect, as previously proposed.

Non-statistical intermolecular energy transfer from vibrationally excited benzene in a mixed nitrogen-benzene bath.

A chemical dynamics simulation was performed to model experiments [N. A. West et al., J. Chem. Phys. 145, 014308 (2016)] in which benzene molecules are vibrationally excited to 148.1 kcal/mol within a N2-benzene bath. A significant fraction of the benzene molecules are excited, resulting in heating of the bath, which is accurately represented by the simulation. The interesting finding from the simulations is the non-statistical collisional energy transfer from the vibrationally excited benzene C6H6 * molecules to the bath. The simulations find that at ∼10-7 s and 1 atm pressure there are four different final temperatures for C6H6 * and the bath. N2 vibration is not excited and remains at the original bath temperature of 300 K. Rotation and translation degrees of freedom of both N2 and C6H6 in the bath are excited to a final temperature of ∼340 K. Energy transfer from the excited C6H6 * molecules is more efficient to vibration of the C6H6 bath than its rotation and translation degrees of freedom, and the final vibrational temperature of the C6H6 bath is ∼453 K, if the average energy of each C6H6 vibration mode is assumed to be RT. There is no vibrational equilibration between C6H6 * and the C6H6 bath molecules. When the simulations are terminated, the vibrational temperatures of the C6H6 * and C6H6 bath molecules are ∼537 K and ∼453 K, respectively. An important question is the time scale for complete energy equilibration of the C6H6 * and N2 and C6H6 bath system. At 1 atm and 300 K, the experimental V-T (vibration-translation) relaxation time for N2 is ∼10-4 s. The simulation time was too short for equilibrium to be attained, and the time for complete equilibration of C6H6 * vibration with translation, rotation, and vibration of the bath was not determined.

A method of extracting speed-dependent vector correlations from 2 + 1 REMPI ion images.

We present analytical expressions for extracting Dixon's bipolar moments in the semi-classical limit from experimental anisotropy parameters of sliced or reconstructed non-sliced images. The current method focuses on images generated by 2 + 1 REMPI (Resonance Enhanced Multi-photon Ionization) and is a necessary extension of our previously published 1 + 1 REMPI equations. Two approaches for applying the new equations, direct inversion and forward convolution, are presented. As demonstration of the new method, bipolar moments were extracted from images of carbonyl sulfide (OCS) photodissociation at 230 nm and NO2 photodissociation at 355 nm, and the results are consistent with previous publications.

Photodissociation dynamics of OCS near 214 nm using ion imaging.

The OCS photodissociation dynamics of the dominant S((1)D2) channel near 214 nm have been studied using velocity map ion imaging. We report a CO vibrational branching ratio of 0.79:0.21 for v = 0:v = 1, indicating substantially higher vibrational excitation than that observed at slightly longer wavelengths. The CO rotational distribution is bimodal for both v = 0 and v = 1, although the bimodality is less pronounced than at longer wavelengths. Vector correlations, including rotational alignment, indicate that absorption to both the 2(1)A' (A) and 1(1)A″ (B) states is important in the lower-j part of the rotational distribution, while only 2(1)A' state absorption contributes to the upper part; this conclusion is consistent with work at longer wavelengths. Classical trajectory calculations including surface hopping reproduce the measured CO rotational distributions and their dependence on wavelength well, though they underestimate the v = 1 population. The calculations indicate that the higher-j peak in the rotational distribution arises from molecules that begin on the 2(1)A' state but make nonadiabatic transitions to the 1(1)A' (X) state during the dissociation, while the lower-j peak arises from direct photodissociation on either the 2(1)A' or the 1(1)A″ states, as found in previous work.

Resolving the energy and temperature dependence of C6H6 (∗) collisional relaxation via time-dependent bath temperature measurements.

The relaxation of highly vibrationally excited benzene, generated by 193 nm laser excitation, was studied using the transient rotational-translational temperature rise of the N2 bath, which was measured by proxy using two-line laser induced fluorescence of seeded NO. The resulting experimentally measured time-dependent N2 temperature rises were modeled with MultiWell based simulations of Collisional Energy Transfer (CET) from benzene vibration to N2 rotation-translation. We find that the average energy transferred in benzene deactivating collisions depends linearly on the internal energy of the excited benzene molecules and depends approximately linearly on the N2 bath temperature between 300 K and 600 K. The results are consistent with experimental studies and classical trajectory calculations of CET in similar systems.

Simultaneous three-dimensional velocimetry and thermometry in gaseous flows using the stereoscopic vibrationally excited nitric oxide monitoring technique.

We present a demonstration of the simultaneous measurement of spatially resolved three-component velocity and temperature in gaseous flow fields using a variant of the vibrationally excited nitric oxide monitoring (VENOM) technique, based on planar laser induced fluorescence and molecular tagging velocimetry methods. Three-component velocity determinations were derived from two-dimensional molecular tagging velocity measurements employing sequential fluorescence image pairs obtained simultaneously by two cameras in stereoscopic configuration. Probing two different rotational states of nitric oxide (X2∏, υ''=1), produced via fluorescence and collisional quenching from initial excitation to the A Σ+2 state, for the sequential velocimetry images allows simultaneous determination of the temperature field. Experimental measurements of velocity and temperature across an oblique shock result in mean values within 21 m/s for the three components of velocity and 20 K for planar temperature when compared to oblique shock calculations.

A unified model for simulating liquid and gas phase, intermolecular energy transfer: N2 + C6F6 collisions.

Molecular dynamics simulations were used to study relaxation of a vibrationally excited C6F6* molecule in a N2 bath. Ab initio calculations were performed to develop N2-N2 and N2-C6F6 intermolecular potentials for the simulations. Energy transfer from "hot" C6F6 is studied versus the bath density (pressure) and number of bath molecules. For the large bath limit, there is no heating of the bath. As C6F6* is relaxed, the average energy of C6F6* is determined versus time, i.e., ⟨E(t)⟩, and for each bath density ⟨E(t)⟩ is energy dependent and cannot be fit by a single exponential. In the long-time limit C6F6 is fully equilibrated with the bath. For a large bath and low pressures, the simulations are in the fixed temperature, independent collision regime and the simulation results may be compared with gas phase experiments of collisional energy transfer. The derivative d[⟨E(t)⟩]/dt divided by the collision frequency ω of the N2 bath gives the average energy transferred from C6F6* per collision ⟨ΔE(c)⟩, which is in excellent agreement with experiment. For the ~100-300 ps simulations reported here, energy transfer from C6F6* is to N2 rotation and translation in accord with the equipartition model, with no energy transfer to N2 vibration. The energy transfer dynamics from C6F6* is not statistically sensitive to fine details of the N2-C6F6 intermolecular potential. Tests, with simulation ensembles of different sizes, show that a relatively modest ensemble of only 24 trajectories gives statistically meaningful results.

Vibrationally excited NO tagging by NO(A²∑⁺) fluorescence and quenching for simultaneous velocimetry and thermometry in gaseous flows.

We present measurements demonstrating simultaneous determination of velocity and temperature using a variant of the Vibrationally Excited Nitric Oxide Monitoring (VENOM) technique that does not employ NO2. The variant is based on tagging by electronic excitation of NO in the A²∑(1/2)⁺ (v'=0)←X2Π1/2(v''=0) band and subsequent formation of vibrationally excited NO(X2Π) by spontaneous emission and collisional quenching. Sequential planar laser-induced fluorescence imaging of the nascent NO(X2Π, v''=1) was used to obtain spatially resolved average streamwise velocity and rotational/translational temperature. The temperature determination using this approach extends the applicability of the VENOM technique to low-density, high-speed flows, where slow thermalization of the tagged molecules represents a limiting factor.

Experimental and theoretical investigation of correlated fine structure branching ratios arising from state-selected predissociation of BrO (A2Π3/2).

We present results for the v'-dependent predissociation dynamics of the BrO (A(2)Π3/2) state using velocity map ion imaging. Correlated fine structure branching ratios, Br((2)P(J)) + O((3)P(J)), have been measured for v' = 5-16 states. The experimental branching ratios are non-statistical and strongly dependent on the initial vibronic state. The current measurements represent an extensive dataset containing rich information about the predissociation dynamics of this system and should provide a stringent test for modern theory. New high level ab initio excited state potentials are presented and have been optimized using experimental v'-dependent predissociation lifetimes and calculated coupling constants. Comparisons between the experimental branching ratios and the predictions based on diabatic and adiabatic limiting models are presented. We find that the adiabatic model is most consistent with the observed trends in the correlated branching ratios, in contrast to previous studies on the related ClO system.

Measuring the internal energies of species emitted from hypervelocity nanoprojectile impacts on surfaces using recalibrated benzylpyridinium probe ions.

We present herein a framework for measuring the internal energy distributions of vibrationally excited molecular ions emitted from hypervelocity nanoprojectile impacts on organic surfaces. The experimental portion of this framework is based on the measurement of lifetime distributions of "thermometer" benzylpyridinium ions dissociated within a time of flight mass spectrometer. The theoretical component comprises re-evaluation of the fragmentation energetics of benzylpyridinium ions at the coupled-cluster singles and doubles with perturbative triples level. Vibrational frequencies for the ground and transition states of select molecules are reported, allowing for a full description of vibrational excitations of these molecules via Rice-Ramsperger-Kassel-Marcus unimolecular fragmentation theory. Ultimately, this approach is used to evaluate the internal energy distributions from the measured lifetime distributions. The average internal energies of benzylpyridinium ions measured from 440 keV Au400(+4) impacts are found to be relatively low (~0.24 eV/atom) when compared with keV atomic bombardment of surfaces (1-2 eV/atom).

Coherence brightened laser source for atmospheric remote sensing.

We have studied coherent emission from ambient air and demonstrated efficient generation of laser-like beams directed both forward and backward with respect to a nanosecond ultraviolet pumping laser beam. The generated optical gain is a result of two-photon photolysis of atmospheric O(2), followed by two-photon excitation of atomic oxygen. We have analyzed the temporal shapes of the emitted pulses and have observed very short duration intensity spikes as well as a large Rabi frequency that corresponds to the emitted field. Our results suggest that the emission process exhibits nonadiabatic atomic coherence, which is similar in nature to Dicke superradiance where atomic coherence is large and can be contrasted with ordinary lasing where atomic coherence is negligible. This atomic coherence in oxygen adds insight to the optical emission physics and holds promise for remote sensing techniques employing nonlinear spectroscopy.

Stereodynamics of multistate roaming.

We present a molecular level description of NO3→ NO + O2 photodissociation for both of the experimentally observed reaction pathways using the results of ion imaging experiments and recent theoretical studies. Vector correlation and Λ doublet propensity measurements have been performed on state-selected NO fragments in order to further characterize the stereodynamics of this reaction. Previous measurements (Grubb et al., Science, 2012, 1075-1078) of relative Λ doublet propensities along with ab initio calculations revealed that both pathways arise from roaming-type mechanisms, but each pathway arises from roaming on a different electronic potential. This model, however, assumes that NO3 dissociation takes place in the molecular plane. In the present paper, we have confirmed this assumption through speed-dependent vector correlation measurements. Strong perpendicular correlations between the velocity vector v and the angular momentum vector j are observed in the NO fragment originating from both pathways, in agreement with a constrained planar dissociation. These results are discussed in light of the absence of vector correlations in other roaming systems, which have previously been characterized by an unconstrained intra-molecular abstraction. We show that geometrical constraints should in fact be quite prevalent in roaming dynamics, and are analogous to the geometrical constraints of the corresponding bimolecular abstraction reaction.