Photolysis Energy Research Articles

POPTARTS: A New Method to Determine Quantum Yields in a Molecular Beam.

A new technique is reported to determine absolute photodissociation quantum yields, ϕdiss, in a molecular beam. The technique relies on a molecule having two available product channels, where a species in channel A can be converted photolytically to a species in channel B. The relative decrease in the species from channel A and the relative increase in species from B provide a direct measure of the relative product yield of each channel, with no external calibration required. In the event that only channels A and B exist, or at least dominate, then the sum rule ϕA + ϕB = 1 can be used to convert relative quantum yields into absolute yields. The technique is demonstrated using the well-understood and characterized photochemistry of HCHO. Formaldehyde photolysis at wavelengths near 310 nm produces either H + HCO (channel A) or H2 + CO (channel B). HCO can then be photolyzed with high efficiency into H + CO. The product state distributions for HCO from channel A, CO from channel B, and CO from the secondary HCO photolysis event are all well-known; this is not a requirement but is utilized here to demonstrate the veracity of the technique. The zero-pressure quantum yields of HCO from HCHO photolysis via the 2341 and 2151 states of HCHO are determined to be 0.66 and 0.74, respectively, which are in excellent agreement with the established quantum yields at atmospheric pressure and support the conclusion that HCHO quantum yields at these photolysis energies are not pressure dependent.

Structural Effects on the Norrish Type I α-Bond Cleavage of Tropospherically Important Carbonyls

Norrish Type I (NTI) α-bond cleavage is the dominant photolysis mechanism in small carbonyls and is an important source of radicals in the troposphere. In nonsymmetric species two cleavages are possible, NTIa and NTIb, forming larger and smaller alkyl radicals, respectively. For a data set of 20 small, atmospherically relevant carbonyls we predict NTIa and NTIb thresholds on the S0, S1, and T1 electronic states. The calculated NTIa T1 thresholds give a mean absolute deviation (MAD) of 5.8 kJ/mol with respect to the available experimental thresholds of five carbonyls. In addition, the intrinsic barrier heights to dissociation on the S0, S1, and T1 electronic states are predicted. We find RI-B2GP-PLYP/def2-TZVP calculations on S0 and unrestricted RI-B2GP-PLYP/def2-TZVP calculations on T1 give MADs of 6.1 kJ/mol for S0 asymptotic energies and 6.3 kJ/mol for S0 → T1 0-0 excitation energies, with respect to available experimental data. A composite method is used to determine S1 thresholds, with bt-STEOM-CCSD/cc-pVQZ calculation of vertical excitation energies and TD-RI-B3LYP/def2-TZVP calculations on S1, which achieves a MAD of 7.2 kJ/mol, with respect to experimental 0-0 excitation energies. Our calculations suggest, with the exception of bifunctional carbonyls and enones, NTI reactions on S1 are unlikely to be important at tropospherically relevant photolysis energies (<400 kJ/mol). In contrast, at these energies almost all possible NTI channels on T1 are open, and all barrierless S0 NTI dissociations are accessible. Our calculations allow a number of structural effects on both 0-0 excitation energies and intrinsic reaction barriers, on a given electronic state, to be elucidated and rationalized.

Roaming Dynamics in the Photodissociation of Formic Acid at 230 nm.

Roaming dynamics is observed in the photodissociation of formic acid (HCOOH) at 230 nm by using the slice imaging method. In combination with rotational state selective (2 + 1) resonance-enhanced multiphoton ionization of the CO fragments, the speed distributions of the CO fragments exhibit a low recoil velocity at low rotational levels of J = 9 and 20, while the velocity distributions of CO at high rotational levels of J = 30 and 48 show a relatively large recoil velocity. The experimental results indicate that the roaming of OH radical should be related with the formation of CO + H2O channel at the present photolysis energy. Unlike the roaming pathways occurring in H2CO that can be described by loose flat potential, our CO speed distribution analysis suggests the presence of a "tight" flat potential in the roaming dynamics of HCOOH molecules.

Impact of heat treatment on NBOHC luminescence of OH-containing and H2-impregnated fused silica for deep-ultraviolet applications

OH-containing and H2-impregnated fused silica is the optical materials of choice for deep-ultraviolet (DUV) applications. Intrinsic and UV laser irradiation induced non-bridging oxygen hole center (NBOHC) defects play a central role in the optical properties of fused silica in the DUV spectra range. Understanding the NBOHC generation mechanism is of great importance to the performance improvement. In this paper, NBOHC-related 650 nm photoluminescence (PL) band is investigated in details by heat-treating the fused silica at different temperature and exciting the PL band at different wavelength. From the 650 nm PL characteristics of un-treated and heat-treated fused silica samples excited at 193 nm, 266 nm, 355 nm, and 532 nm, it is found that the 650 nm PL band of un-treated fused silica is excited at 193 nm and 266 nm mainly via a two-photon process, and cannot be excited with 355 nm and 532 nm. The un-treated fused silica also presented a reversible time delay (annealing) in 650 nm PL intensity following an abrupt change of excitation fluence at 193 nm, due to the recombination of NBOHCs with impregnated H2. On the other hand, for the heat-treated fused silica, the 650 nm PL band is excited by a combination of one- and two-photon processes at 193 nm and 266 nm with the one-photon process dominating, and by the one-photon excitation process at 355 nm and 532 nm. The quantum yield of 650 nm PL band decreases with the decreasing excitation photon energy. From these experimental results it is confirmed with no doubt that in un-treated fused silica NBOHCs are produced by 193 nm and 266 nm laser irradiation induced photolysis of an Si‒OH group via a two-photon process, with a minimum photolysis energy between 7.0 eV and 7.9 eV. In heat-treated fused silica NBOHCs are produced by heat treatment induced breakage of Si‒OH bonds. Heat treatment also removed totally the impregnated H2 in fused silica, that makes the heat-treatment produced NBOHCs become stable and show one-photon excited 650 nm PL band when excited at 193 nm, 266 nm, 355 nm, and 532 nm. In contrary to the un-treated fused silica, the heat-treated fused silica presented no reversible time delay in 650 nm PL intensity following the abrupt change of excitation fluence at 193 nm, due to the total removal of H2 in fused silica and the absence of recombination of NBOHCs with H2.

Exit-channel recoil resonances by imaging the photodissociation of single quantum-state-selected OCS molecules

In a recent letter [Phys. Rev. Lett. 118, 253001 (2017)] we have described how studies of the recoil velocity distribution in the photodissociation of OCS in the energy interval 42 600--42 900 ${\mathrm{cm}}^{\ensuremath{-}1}$ revealed an unexpected behavior: the recoil velocity distribution of only the lowest-kinetic-energy photofragments exhibited rapid, resonantlike variations with energy and caused complete inversion of the recoil direction. Periodic orbit analysis and quantum nonadiabatic calculations unveiled the existence of a resonance state localized at large bending angles towards the exit of the dissociation channel. In this article, we present an extensive theoretical study and we show how the fingerprints of these resonances are identified by the analysis of the nonadiabatic transitions and the stereodynamics of photofragments trajectories. Additionally, the experimental study is extended to a second photolysis energy region, 43 300--43 650 ${\mathrm{cm}}^{\ensuremath{-}1}$, where a similar rapid variation of the recoil direction is detected. The energy separation between this second resonance region and the one previously reported is $\ensuremath{\sim}800\phantom{\rule{0.28em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$, which is twice the calculated period of the localized resonant state, offering a second point of convergence between the experiment and the theory.

Photodissociation dynamics of propanal and isobutanal: The Norrish Type I pathway

The Norrish Type I photodissociation of two aliphatic aldehydes, propanal and isobutanal, has been investigated using velocity-map imaging. The HCO photoproduct of this reaction was probed using a 1+1 resonance-enhanced multiphoton ionization scheme via the 3p2Π Rydberg state. The velocity map images of HCO+ were collected across a range of photolysis energies for both species from 30 500 to 33 000 cm-1 (λ = 312-327 nm). The corresponding translational energy distributions show that the majority of the available energy goes into the translational motion of the products (55%-68%) with this fraction increasing as the T1 barrier is approached. Analysis of the translational energy distributions was also used to determine the aldehyde α C-C bond dissociation energies which were found to be 339.8 ± 2.5 and 331.2 ± 2.5 kJ/mol for propanal and isobutanal, respectively. These values were also found to be in good agreement with the computed dissociation energies using G4 and CCSD(T)/aug-cc-pVTZ//M062X/aug-cc-pVTZ levels of theory. Furthermore, these dissociation energies, combined with the known ΔfH (0 K) of the reaction products, provided the ΔfH (0 K) of propanal and isobutanal which were calculated to be -167.3 ± 2.5 and -184.0 ± 2.5 kJ/mol, respectively.

Photodissociation of acetone from 266 to 312 nm: Dynamics of CH3 + CH3CO channels on the S0 and T1 states.

The photodissociation dynamics of acetone (CH3)2CO, cooled in a molecular beam, have been explored over the wavelength range 266-312 nm. Nascent CH3 fragments were detected by resonance-enhanced multiphoton ionization, followed by mass-selected ion imaging. For photolysis at λ = 306 nm, the image shows a sharp ring, which, when converted to a translational energy distribution, reveals a narrow Gaussian peak with a maximum at 90% of the available energy. As the photolysis energy is increased, the distribution slowly broadens and shifts to higher recoil translational energy. The fraction of available energy in translation energy decreases in favour of internal energy of the CH3CO fragment. These observations are consistent with a dynamical model in which the energy of the exit channel barrier on the T1 surface evolves mostly into relative translational energy. Energy in excess of the barrier is partitioned statistically into all degrees of freedom. No evidence was found for any other dynamical pathway producing CH3 fragments, including reaction on S0 or S1, for dissociation between 306 and 266 nm. For λ > 306 nm, a diffuse, slow recoil component to the image appears. The translational energy distribution for this component is fit well by a statistical prior distribution of energy. We attribute this component to dissociation on the S0, ground state surface; to our knowledge, this is the first direct observation of this channel. The appearance of S0 dynamics and the disappearance of the T1 component are consistent with previously inferred barrier height on T1 for the production of CH3CO + CH3. The possible atmospheric implications of our findings are discussed.

Dynamics and yields for CHBrCl2 photodissociation from 215-265 nm.

We investigate the Ã-band photodissociation of CHBrCl2 at 215, 225, 235, 245, 255, and 265 nm. Following C-Br bond cleavage, resonance enhanced multiphoton ionization and time of flight mass spectrometry provide selective detection of the two product channels, from which we quantify the relative quantum yield of Br/Br* production. Velocity-map imaging of the photofragments allows us to determine the energy partitioning as a function of the photolysis energy for different exit channels. The anisotropy present in the imaging data suggests that absorption to the 3Q0+(A') state is important throughout the entire region we study, though competition with other excited states is evident. The 3Q0+(A') state forms an avoided crossing with the 1Q1(A') state, and we find that the propensity for adiabatic passage through this crossing region dictates the Br yield at longer wavelengths. At shorter wavelengths, Br production from excited states not subject to the crossing is more evident. While we find that spin-orbit excitation comes largely at the expense of the CHCl2 internal energy, both channels still produce highly excited CHCl2 photofragments. Impulsive modeling and comparison with similar halomethane dissociations suggests that a high degree of rotational excitation is present, dictated by the torque inherent in Cs-symmetry dissociation and the angular dependence of the potential.

Photodissociation dynamics of HOD via the B̃ ((1)A1) electronic state.

Photodissociation dynamics of HOD from the B̃ state has been studied using H/D atom Rydberg "tagging" time-of-flight technique. Both the OD + H and OH + D channels have been investigated. Product kinetic energy distributions, internal state distributions of the OD/OH product, as well as the OD/OH quantum state specific angular anisotropy parameters have been determined. Overall, the photodissociation dynamics of HOD via the B̃ state is qualitatively similar to that of the H2O and D2O, with quantitative differences arising probably from the change in masses. At different photolysis energies, similar rovibrational distributions and state-resolved angular distributions have been observed for the OH/OD(X) product, while remarkable differences have been observed in the rovibrational distributions and state-resolved angular distributions of the OH/OD(A) product.

Chemistry of impact events on the Moon

Based on the equilibrium thermochemical approach and quenching theory, the formation of Na-, K-, Li-, Si-, Ca-, Al-, Mg-, and Fe-bearing molecules and dust particles in impact-produced clouds formed after collisions between meteoroids and the Moon is considered. Photolysis lifetimes and energies of photolysis products of oxides and hydroxides of the main elements are estimated. The estimated fraction of uncondensed species, and list of the main molecules and their properties regarding photolysis during impact processes may be useful for the analysis of future observations of atoms of alkali and refractory elements in the exospheres of the Moon and Mercury.

Three-state surface hopping calculations of acetaldehyde photodissociation to CH3 + HCO on ab initio potential surfaces

We report Trajectory Surface Hopping (TSH) calculations of CH3CHO photodissociation involving three electronic states, S1, T1, and S0, with a focus on the radical products CH3 + HCO, which can be formed from both T0 and S0. We use previously reported potential energy surfaces and spin-orbit couplings for T1 and S0 and report a new potential and spin-orbit coupling for S1 here. Roughly 32 000 trajectories are performed at energies corresponding to seven photolysis wavelengths between 372 and 230 nm. Motivated by recent experiments, we examine the branching ratio of the T1 to S0 pathways as a function of photolysis energy. We also present the relative translational energy and CH3 vibrational energy distributions from these pathways at a photolysis energy of 100 kcal mol(-1), formed from both the T1 and S0 potentials. As with standard quasiclassical trajectory calculations, violation of zero-point energy for products also occurs in TSH calculations. This is shown to be a serious issue for this branching ratio and one of several methods considered to deal with this issue is shown to give satisfactory results.

Photodissociation dynamics of H2O: Effect of unstable resonances on the $\tilde B\,^{1}{\rm \!A}_{1}$B̃1A1 electronic state

We report a tunable vacuum ultraviolet photodissociation study of H(2)O from different unstable resonances in the B̃(1)A(1) electronic state, using the H-atom Rydberg tagging technique. The quantum state resolved OH product translational energy distributions and angular distributions have been measured. Experimental results illustrate, for the first time, that excitation to the different unstable resonances has very different effect on the OH(X) and OH(A) product channels. The OH(X) product rotational distributions vary only slightly, while the OH(A) product rotational distributions and state-resolved angular distributions change dramatically as the photolysis energy increases. Effect of parent rotational excitation on the OH(A) product has also been observed. Through careful simulations to the experimental spectra, OH(A)∕OH(X) branching ratios have been determined at five photolysis wavelengths. The general agreement between theory and experiment in the branching ratios is good. The branching ratios for the OH(A) product from different parent rotational levels are close to the nuclear spin-statistics value, which is also consistent with the extremely low rotational temperature of the H(2)O beam in the current experiment.

Production of cold bromine atoms at zero mean velocity by photodissociation

The production of a translationally cold (T < 1 K) sample of bromine atoms with estimated densities of up to 10(8) cm(-3) using photodissociation is presented. A molecular beam of Br(2) seeded in Kr is photodissociated into Br + Br* fragments, and the velocity distribution of the atomic fragments is determined using (2 + 1) REMPI and velocity map ion imaging. By recording images with varying delay times between the dissociation and probe lasers, we investigate the length of time after dissociation for which atoms remain in the laser focus, and determine the velocity spread of those atoms. By careful selection of the photolysis energy, it is found that a fraction of the atoms can be detected for delay times in excess of 100 μs. These are atoms for which the fragment recoil velocity vector is directly opposed and equal in magnitude to the parent beam velocity leading to a resultant lab frame velocity of approximately zero. The FWHM velocity spreads of detected atoms along the beam axis after 100 μs are less than 5 ms(-1), corresponding to temperatures in the milliKelvin range, opening the possibility that this technique could be utilized as a slow Br atom source.

Branching ratios and anisotropy parameters in ICl photolysis from 400 to 570 nm using slice imaging

ICl photolysis in the visible region of the spectrum (400-570 nm) is studied using the slice imaging technique. The Cl((2)P(1/2))/Cl((2)P(3/2)) branching ratio between the I((2)P(3/2))+Cl((2)P(3/2)) and I((2)P(3/2))+Cl((2)P(1/2)) channels is extracted from the iodine photofragment images and it is found to range from 0 to 2.5, rising from 570 to 490 nm and dropping at higher photolysis energies. The I+Cl angular distribution exhibits a similar trend, changing from purely perpendicular at 570 nm to isotropic at 545 nm, fairly parallel at 490 nm and again perpendicular at 440 nm. Following previous work, we discuss these changes in light of avoided curve crossing and determine the crossing probability as a function of wavelength. The angular anisotropy parameter beta of the second channel ranges between 0.6 and 1.4.

Photodissociation of NO2 in the (2) B22 state: The O(D12) dissociation channel

Direct current slice and crush velocity map imaging has been used to probe the photodissociation dynamics of nitrogen dioxide above the second dissociation limit. The paper is a companion to a previous publication [J. Chem. Phys. 128, 164318 (2008)] in which we reported results for the O((3)P(J)) + NO((2)Pi(Omega)) adiabatic product channel. Here we examine the O((1)D(2)) + NO((2)Pi(Omega)) diabatic product channel at similar excitation energies. Using one- and two-color imaging experiments to observe the velocity distributions of state selected NO fragments and O atoms, respectively, we are able to build a detailed picture of the dissociation dynamics. We show that by combining the information obtained from velocity map imaging studies with mass-resolved resonantly enhanced multiphoton ionization spectroscopy it is possible to interpret and fully assign the NO images. By recording two-color images of the O((1)D(2)) photofragments with different polarization combinations of the pump and probe laser fields we also measure the orbital angular momentum alignment in the atomic fragment. We find that the entire O((1)D(2)) photofragment distribution is similarly aligned with most of the population in the M(J) = +/-1 magnetic sublevels. The similarity of the fragment polarizations is interpreted as a signature of all of the O((1)D(2)) atoms being formed via the same avoided crossing. At the photolysis energy of 5.479 52 eV we find that the NO fragments are preferentially formed in v = 1 and that the vibrationally excited fragments exhibit a bimodal rotational distribution. This is in contrast to the unimodal rotational profile of the NO fragments in v = 0. We discuss these observations in terms of the calculated topology of the adiabatic potential energy surfaces and attribute the vibrational inversion and rotational bimodality of the v = 1 fragments to the symmetric stretch and bending motion generated on excitation to the (2) (2)B(2) state.

UV Photodissociation Dynamics of Nitric Acid: The Hydroxyl Elimination Channel

Sliced velocity mapping ion imaging technique was employed to investigate the dynamics of the hydroxyl elimination channel in the photodissociaiton of nitric acid in the ultraviolet region. The OH product was detected by (2+1) resonance enhanced multiphoton ionization via the D2 electronic state. The total kinetic energy spectra of the OH+NO2 channel from the photolysis of HONO2 show that both NO2(X2A1) and NO2(AB2) channels are present, suggesting that both 11A and 21A excited electronic states of HONO2 are involved in the excitation. The parallel angular distributions suggest that the dissociation of the nitric acid is a fast process in comparison with the rotational period of the HNO3 molecule. The anisotropy parameter for the hydroxyl elimination channel is found to be dependent on the OH product rotational state as well as the photolysis energy.

Photochemical formation of HCO and CH3 on the ground S (A1′) state of CH3CHO

The dynamics of the photodissociation of CH(3)CHO into CH(3) + HCO products have been investigated at energies between 30,953 and 31,771 cm(-1), spanning the threshold for radical production on the triplet (T(1)) surface. A barrierless pathway to CH(3) + HCO radical products formed on the ground state (S(0)) surface was discovered and established to be an important reaction channel in acetaldehyde photodissociation throughout this wavelength range. HCO laser induced fluorescence (LIF) spectra recorded from CH(3)CHO dissociated above and below the T(1) barrier energy are quite different; HCO produced on S(0) yields a more congested LIF spectrum with sharp rotational transitions, while HCO formed on the T(1) surface displays fewer, more intense, Doppler-broadened lines. These differences have been further explored in the populations of the HCO K(a) = 1 doublets. Despite the upper and lower levels being almost isoenergetic, HCO formed on T(1) preferentially populates the upper K(c) state due to the geometry of the T(1) transition state structure. In contrast, HCO formed on S(0) produces equal population in each of the upper and lower K(a) = 1 components. Product state distributions (PSDs) showed that HCO formed on S(0) is born with an approximately statistical distribution of population in the available product states, modeled well by phase space theory. HCO formed on the T(1) surface, in contrast, has a PSD that can be characterized as arising from "impulsive" dynamics. Previous discrepancies in the height of the T(1) barrier are discussed following the observation that, once the T(1) channel is energetically accessible, there is competition between the S(0) and T(1) pathways, with the dominance of the triplet channel increasing with increasing photolysis energy.

UV Photodissociation Dynamics of HN3 in 190-248 nm

The H+N3 channel in the ultraviolet photodissociation of HN3 has been investigated from 190 nm to {248 nm} using the high-n Rydberg H-atom time-of-flight technique. Product translational energy distributions as well as product angular anisotropy parameters were determined for the H+N3 channel at different photolysis wavelengths. N3 vibrational state distribution has also been derived from the product translational energy distribution at these wavelengths. Above photolysis wavelength 225 nm, HN3 predominantly dissociate through the repulsive state. Below 225 nm, a new slow channel starts to appear at 220 nm in addition to the existing channel. This channel is attributed to a ring closure dissociation channel to produce the cyclic N3 product. As photolysis energy increases, this new channel becomes more important.

Photolysis of allene and propyne in the 7–30eV region probed by the visible fluorescence of their fragments

The photolysis of allene and propyne, two isomers of C(3)H(4), has been investigated in the excitation energy range of 7-30 eV using vacuum ultraviolet synchrotron radiation. The visible fluorescence excitation spectra of the excited neutral photofragments of both isomers were recorded within the same experimental conditions. Below the first ionization potential (IP), this fluorescence was too weak to be dispersed and possibly originated from C(2)H or CH(2) radicals. Above IP, three excited photofragments have been characterized by their dispersed emission spectra: the CH radical (A (2)Delta-X (2)Pi), the C(2) radical (d (3)Pi(g)-a (3)Pi(u), "Swan's bands"), and the H atom (4-2 and 3-2 Balmer lines). A detailed analysis of the integrated emission intensities allowed us to determine several apparition thresholds for these fragments, all of them being interpreted as rapid and barrierless dissociation processes on the excited potential energy surfaces. In the low energy range explored in this work, both isomers exhibit different intensity distributions in their fragment emission as a function of the photolysis energy, indicating that mutual allene<-->propyne isomerization is not fully completed before dissociation occurs. The effect of isomerization on the dissociation into excited fragments is present in the whole excitation energy range albeit less important in the 7-16 eV region; it gradually increases with increasing excitation energy. Above 19 eV, the fragment distribution is very similar for the two isomers.

DC slice ion imaging of the ultraviolet photodissociation of BrCN

The photodissociation of jet-cooled BrCN molecules has been investigated by DC slice ion imaging of the Br atom product at wavelengths of 193 and 234 nm. The images reveal that both the ground state ( 2P 3/2) and spin–orbit excited ( 2P 1/2) bromine atoms are produced at both photolysis energies studied. The translational energy measurements show that at 193 nm the CN fragments are vibrationally cold, while the vibrational excitation is much higher in dissociation at 234 nm. Furthermore, the CN vibrational excitation in the spin–orbit excited Br product channel is higher at both wavelengths studied.