Photofragment Translational Spectroscopy Research Articles

Photodissociation dynamics of the ethyl radical via the Ã2A'(3s) state: H-atom product channels and ethylene product vibrational state distribution.

The photodissociation dynamics of jet-cooled ethyl radical (C2H5) via the Ã2A'(3s) states are studied in the wavelength region of 230-260nm using the high-n Rydberg H-atom time-of-flight (TOF) technique. The H + C2H4 product channels are reexamined using the H-atom TOF spectra and photofragment translational spectroscopy. A prompt H + C2H4(X̃1Ag) product channel is characterized by a repulsive translational energy release, anisotropic product angular distribution, and partially resolved vibrational state distribution of the C2H4(X̃1Ag) product. This fast dissociation is initiated from the 3s Rydberg state and proceeds via a H-bridged configuration directly to the H + C2H4(X̃1Ag) products. A statistical-like H + C2H4(X̃1Ag) product channel via unimolecular dissociation of the hot electronic ground-state ethyl (X̃2A') after internal conversion from the 3s Rydberg state is also examined, showing a modest translational energy release and isotropic angular distribution. An adiabatic H + excited triplet C2H4(ã3B1u) product channel (a minor channel) is identified by energy-dependent product angular distribution, showing a small translational energy release, anisotropic angular distribution, and significant internal excitation in the C2H4(ã3B1u) product. The dissociation times of the different product channels are evaluated using energy-dependent product angular distribution and pump-probe delay measurements. The prompt H + C2H4(X̃1Ag) product channel has a dissociation time scale of <10ps, and the upper bound of the dissociation time scale of the statistical-like H + C2H4(X̃1Ag) product channel is <5ns.

Ethylcarbene versus Direct Propene Formation in the Near-UV Photodissociation of Ethylketene

The competing pathways in the photodissociation of gaseous ethylketene at excitation wavelengths of 320.0, 340.0, and 355.1 nm were studied using photofragment translational energy spectroscopy. The primary dissociation channel was C═C bond fission producing ethylcarbene (CH3CH2CH; also known as propylidene) and CO. Product translational energy distributions are consistent with theoretical predictions that ground state ethylcarbene lies ∼34 kJ/mol higher in energy than its isomer dimethylcarbene (CH3CCH3). A second dissociation channel involved direct formation of propene prior to or concurrent with CO elimination. The measured product branching ratios indicate that the effective potential energy barrier for the direct propene channel lies below the energetic threshold for ethylcarbene formation. A minor C-C bond fission channel was also observed, leading to CH3 + CH2CHCO products. Comparisons are made to the results of our recent studies of methylketene and dimethylketene photodissociation.

Dimethylcarbene versus Direct Propene Formation in Dimethylketene Photodissociation.

Highly reactive carbenes are usually produced by photolysis of ketenes, diazoalkanes, or diazirines. Sequential kinetic pathways for deactivation of nascent carbenes usually involve bimolecular reactions in competition with isomerization producing stable products such as alkenes. However, the direct photolytic production of stable products, effectively bypassing formation of free carbenes, has been postulated for over 50 years but remains very poorly understood. Often termed "rearrangement in the excited state" (RIES), examples include 1,2-hydrogen migration within photoexcited carbene precursors yielding alkenes and the Wolff rearrangement in photogenerated carbonyl-substituted carbenes producing ketenes. In this study, the two competing CO elimination channels from photoexcited gaseous dimethylketene, producing dimethylcarbene and propene, were studied as a function of electronic excitation energy, under collision-free conditions, by using photofragment translational energy spectroscopy with vacuum ultraviolet photoionization of the products. A significant fraction of the dimethylcarbene → propene isomerization exothermicity (∼300 kJ/mol) was released as propene + CO translational energy, indicating that propene is formed prior to or concurrent with CO elimination. An increase in the propene yield with increasing excitation energy suggests that the effective potential energy barrier for this channel lies ∼24 kJ/mol above the energetic threshold for dimethylcarbene formation via C═C bond fission. Possible mechanisms for direct propene elimination are discussed in light of the observed energy dependence for the competing pathways.

Photodissociation Dynamics of the Cyclohexyl Radical from the 3p Rydberg State at 248 nm.

The photodissociation of jet-cooled cyclohexyl was studied by exciting the radicals to their 3p Rydberg state by using 248 nm laser light and detecting photoproducts by photofragment translational spectroscopy. Both H atom loss and dissociation to heavy fragment pairs are observed. The H atom loss channel exhibits a two-component translational energy distribution. The fast photoproduct component is attributed to impulsive cleavage directly from an excited state, likely the Rydberg 3s state, forming cyclohexene. The slow component is due to statistical decomposition of hot cyclohexyl radicals that internally convert to the ground electronic state prior to H atom loss. The fast and slow components are present in an ∼0.7:1 ratio, similar to findings in other alkyl radicals. Internal conversion to the ground state also leads to ring-opening followed by dissociation to 1-buten-4-yl + ethene in comparable yield to H-loss, with the C4H7 fragment containing enough internal energy to dissociate further to butadiene via H atom loss. A very minor ground-state C5H8 + CH3 channel is observed, attributed predominantly to 1,3-pentadiene formation. The ground-state branching ratios agree well with RRKM calculations, which also predict C4H6 + C2H5 and C3H6 + C3H5 channels with similar yield to C5H8 + CH3. If these channels were active, it was at levels too low to be observed.

Photodissociation Dynamics of H2O via the Ẽ' (1B2) Electronic State.

Photodissociation dynamics of H2O via the Ẽ'1B2 state were studied using the high-resolution H atom photofragment translational spectroscopy method, in combination with the tunable vacuum ultraviolet free electron laser (VUV FEL). The measured translational energy spectra allow us to determine the respective quantum state population distributions for the nascent OH(X2Π) and OH(A2Σ+) photofragments. Analyses of the quantum state population distributions show both the ground and electronically excited OH fragments to be formed with moderate vibrational excitation but with highly rotational excitation. Unlike the dissociation via the lower-lying electronic states, where OH(X) is the major fragment, the OH(A) products are predominant via the Ẽ' state. These products are mainly ascribed to a fast dissociation on the B̃1A1 state surface after nonadiabatic transitions from the initial excited Ẽ' state to the B̃ state. Meanwhile, another dissociation pathway from the Ẽ' state to the 1B2 3pb2 state, followed by coupling to the 1A2 3pb2 state, is also observed, which yields the OH(X) + H and O(3P) + 2H products.

Effects of Ring Fluorination on the Ultraviolet Photodissociation Dynamics of Phenol.

The dynamics of photoinduced O-H bond fission in five fluorinated phenols (2-fluorophenol, 3-fluorophenol, 2,6-difluorophenol, 3,4,5-trifluorophenol, and pentafluorophenol) have been investigated by H Rydberg atom photofragment translational spectroscopy following excitation at many wavelengths in the range 220 ≤ λ ≤ 275 nm. The presence of multiple fluorine substituents reduces the efficiency of O-H bond fission (by tunneling) from the first excited (11ππ*) electronic state, whereas all bar the perfluorinated species undergo O-H bond fission when excited at shorter wavelengths (to the 21ππ* state). As in bare phenol, O-H bond fission is deduced to occur by non-adiabatic coupling at conical intersections between the photoprepared "bright" ππ* states and the 11πσ* potential energy surface. In all cases, the fluorophenoxyl photoproducts are found to be formed in a range of vibrational levels, all of which include an odd number of quanta (typically one) in an out-of-plane (a″) vibrational mode; this product vibration is viewed as a legacy of the parent out-of-plane motions that promote non-adiabatic coupling to the dissociative 11πσ* potential. The radical products also show activity in in-plane vibrations involving coupled (both in- and out-of-phase) C-O and C-F wagging motions, which can be traced to the impulse between the recoiling O and H atoms and, in detail, are sensitive to the presence (or not) of an intramolecular F···H-O hydrogen bond. Upper limit values for the O-H bond dissociation energies are reported for all molecules studied apart from pentafluorophenol.

Subpicosecond HI elimination in the 266 nm photodissociation of branched iodoalkanes.

The 266 nm photodissociation dynamics of 1-iodopropane and 2-iodopropane were studied using photofragment translational energy spectroscopy using vacuum ultraviolet (VUV) photoionization and electron impact ionization detection of products. The photochemistry of 1-iodopropane was found to be similar to that of iodomethane and iodoethane, with dominant production of I*(2P1/2), and no evidence (<0.21%) for HI + alkene formation. Significantly different behavior was observed for 2-iodopropane, with dominant production of ground state I(2P3/2), and a HI yield >10.5%. The anisotropy (β) parameters for all channels approached the limiting value of 2.0, indicating that 1,2-HI elimination occurs on subpicosecond timescales, like direct C-I bond fission, following excitation to 3Q0. The HI translational energy and angular distributions were similar to those for I(2P3/2), suggesting that motion of the heavy I atom in HI is largely derived from the repulsive nature of the 1Q1 surface correlating to R + I with the light H atom picked up by ground state I late in the exit channel producing highly vibrationally excited HI.

Photodissociation of iso-propoxy (i-C3H7O) radical at 248 nm.

Photodissociation of the i-C3H7O radical is investigated using fast beam photofragment translational spectroscopy. Neutral i-C3H7O radicals are produced through the photodetachment of a fast beam of i-C3H7O- anions and are subsequently dissociated at 248 nm (5.0 eV). The dominant product channels are CH3 + CH3CHO and OH + C3H6 with some contribution from H + C3H6O. The CH3 and H loss channels are attributed to dissociation on the ground electronic state of i-C3H7O, but in a nonstatistical manner because calculated RRKM dissociation rates exceed the rate of energy randomization. Translational energy and angular distributions for OH loss are consistent with ground state dissociation, but the branching ratio for this channel is considerably higher than predicted from RRKM rate calculations. Additionally, i-C3H7O undergoes three-body fragmentation to CH3 + CH3 + HCO and CH3 + CH4 + CO. These three-body channels are attributed to dissociation of i-C3H7O to CH3 + CH3CHO, followed by secondary dissociation of CH3CHO on its ground electronic state.

Multiphoton dissociation dynamics of the indenyl radical at 248 nm and 193 nm.

Photofragment translational spectroscopy is used to investigate the unimolecular photodissociation of the indenyl radical (C9H7). C9H7 radicals are generated by photodetachment of C9H7 - anions and are dissociated at 248 nm (5.00 eV) and 193 nm (6.42 eV). The following product channels are definitively observed at both wavelengths: C2H2 + C7H5, C2H2 + C3H3 + C4H2, and C2H2 + C2H2 + C5H3. The three-body product channels are energetically inaccessible from single photon excitation at either dissociation wavelength. This observation, in combination with calculated dissociation rates and laser power studies, implies that all dissociation seen in this experiment occurs exclusively through multiphoton processes in which the initial C9H7 radical absorbs two photons sequentially prior to dissociation to two or three fragments. The corresponding translational energy distributions for each product channel peak well below the maximum available energy for two photons and exhibit similar behavior regardless of dissociation wavelength. These results suggest that all products are formed by internal conversion to the ground electronic state, followed by dissociation.

H atom Product Channels in the Ultraviolet Photodissociation of the 2-Propenyl Radical.

The H atom product channels in the ultraviolet photodissociation of 2-propenyl (CH2CCH3) radical were investigated in the wavelength region 224-248 nm using photofragment translational spectroscopy. The CH2CCH3 radicals were generated by 193 nm photodissociation of 2-chloropropene and 2-bromopropene precursors. The H atom photofragment yield spectra from both precursors revealed a broad feature peaking near 232 nm. The translational energy distributions of the H + C3H4 products peaked around 7-8 kcal/mol and extended close to the maximum excess energy. The fraction of the total available energy released as products' translation was nearly a constant (∼0.16 using the 2-chloropropene precursor and ∼0.18 using the 2-bromopropene precursor) in the wavelength range 224-248 nm. The angular distribution of the H atom product was isotropic. Quasi-classical trajectory (QCT) calculations were performed on the ground-state potential energy surface of CH2CCH3 for its decomposition at a 124 kcal/mol excitation energy (equivalent to 230 nm photolysis photon energy). The calculations yielded branching ratios for different dissociation product channels, 32% H + allene, 35% H + propyne, 0.5% H + cyclopropene, and 32% methyl + acetylene. The experimental and QCT translational energy distributions of the H atom loss channels qualitatively agreed, consistent with the main H atom product channels being the H + allene and H + propyne dissociations. The time scale of the 2-propenyl dissociation on the ground electronic state was calculated to be ∼2 ps, smaller compared to that of the overall UV photodissociation (≥10 ps, implied on the basis of the isotropic H atom product angular distribution). The mechanism of the UV photodissociation of 2-propenyl is consistent with unimolecular dissociation proceeding on the ground electronic state after internal conversion of the electronic excited states.

Triplet vs πσ* state mediated N-H dissociation of aniline.

UV-excited aromatic molecules with N-H/O-H moieties often possess an important nonradiative relaxation pathway, from an optically bright ππ* state to a dark dissociative πσ* state. We apply a new time-selected photofragment translational spectroscopy method to disclose a previously unknown triplet-mediated N-H dissociation of aniline prevented by the multiphoton dissociative ionization in conventional methods. We further determined the branching fractions of aniline dissociated in the πσ*, triplet, and ground states at 248 nm. Additionally, we selectively captured the population changes in the singlet and triplet states with ionization from different laser wavelengths, 355 or 266 nm, in time-resolved photoion yields. The combination of experimental data enables us to uniquely determine the relative ionization cross sections of the singlet and triplet states at an ionization laser wavelength of 266 nm and allows us to extensively measure the rate constants of intersystem crossing and the branching fractions at various excitation wavelengths.

Photodissociation dynamics of the methylsulfinyl radical at 248 nm

The photodissociation dynamics of jet-cooled methylsulfinyl radicals, CH3SO, at 248 nm have been investigated using molecular beam photofragment translational spectroscopy. The primary channel is CH3S + O, which occurs via the initially prepared excited CH3SO state by rapid cleavage of the S-O bond to produce ground state products. The minor SO + CH3 channel has two components in comparable proportions: a fast feature corresponding to rapid C-S cleavage on the excited state to produce CH3 and electronically excited SO, and a slow feature due to internal conversion of CH3SO followed by statistical dissociation on the ground electronic state. Statistical ground state dissociation also produces small amounts of CH2SO, likely sulfine, and H-atoms.

Fast beam photofragment translational spectroscopy of the phenoxy radical at 225 nm, 290 nm, and 533 nm.

Photodissociation of the phenoxy radical (C6H5O) is investigated using fast beam photofragment translational spectroscopy. Phenoxy radicals are generated through photodetachment of phenoxide anions (C6H5O-) at 532 nm. Following photoexcitation of the radicals at 225 nm (5.51 eV), 290 nm (4.27 eV), or 533 nm (2.33 eV), photofragments are collected in coincidence to determine their masses, translational energy, and scattering angle for each dissociation event. Two-body dissociation yields exclusively CO + C5H5, and three-body dissociation to CO + C2H2 + C3H3 and CO + C5H4 + H is also seen at the two higher energies. The translational energy distributions for two-body dissociation suggest that dissociation occurs via internal conversion to the ground electronic state followed by statistical dissociation. The absorption of an additional 532 nm photon in the photodetachment region provides some C6H5O radicals with an additional 2.33 eV of energy, leading to much of the two-body dissociation observed at 533 nm and the three-body dissociation at the two higher excitation energies.

Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase.

The ultraviolet (UV) photodissociation of gas-phase methimazole has been investigated by H Rydberg atom photofragment translational spectroscopy methods at many wavelengths in the range of 222.5-275 nm and by complementary electronic structure calculations. Methimazole is shown to exist predominantly as the thione tautomer, 1-methyl-2(3 H)-imidazolinethione, rather than the commonly given thiol form, 2-mercapto-1-methylimidazole. The UV absorption spectrum of methimazole is dominated by the S4 ← S0 transition of the thione tautomer, which involves electron promotion from an a' (p y) orbital localized on the sulfur atom to a σ* orbital localized around the N-H bond. Two H atom formation pathways are identified following UV photoexcitation. One, involving prompt, excited-state N-H bond fission, yields vibrationally cold but rotationally excited methimazolyl (Myl) radicals in their first excited (Ã) electronic state. The second yields H atoms with an isotropic recoil velocity distribution peaking at low kinetic energies but extending to the energetic limit allowed by energy conservation given a ground-state dissociation energy D0(Myl-H) ∼24 000 cm-1. These latter H atoms are attributed to the unimolecular decay of highly vibrationally excited S0 parent molecules. The companion electronic structure calculations provide rationales for both fragmentation pathways and the accompanying product energy disposals and highlight similarities and differences between the UV photochemistry of methimazole and that of other azoles (e.g., imidazole) and with molecules like thiourea and thiouracil that contain similar N-C═S motifs.

Excited-state dissociation dynamics of phenol studied by a new time-resolved technique

Phenol is an important model molecule for the theoretical and experimental investigation of dissociation in the multistate potential energy surfaces. Recent theoretical calculations [X. Xu et al., J. Am. Chem. Soc. 136, 16378 (2014)] suggest that the phenoxyl radical produced in both the X and A states from the O-H bond fission in phenol can contribute substantially to the slow component of photofragment translational energy distribution. However, current experimental techniques struggle to separate the contributions from different dissociation pathways. A new type of time-resolved pump-probe experiment is described that enables the selection of the products generated from a specific time window after molecules are excited by a pump laser pulse and can quantitatively characterize the translational energy distribution and branching ratio of each dissociation pathway. This method modifies conventional photofragment translational spectroscopy by reducing the acceptance angles of the detection region and changing the interaction region of the pump laser beam and the molecular beam along the molecular beam axis. The translational energy distributions and branching ratios of the phenoxyl radicals produced in the X, A, and B states from the photodissociation of phenol at 213 and 193 nm are reported. Unlike other techniques, this method has no interference from the undissociated hot molecules. It can ultimately become a standard pump-probe technique for the study of large molecule photodissociation in multistates.

Photodissociation of the Cyclopentadienyl Radical at 248 nm.

The photodissociation of jet-cooled cyclopentadienyl radicals, c-C5H5, at 248 nm was studied using photofragment translational spectroscopy. Two dissociation channels were observed: H + C5H4 and C3H3 + C2H2. The C5H4 fragment was identified as ethynylallene by its ionization energy. The translational energy distribution determined for each channel suggests that both dissociation mechanisms occur via internal conversion to the ground electronic state followed by intramolecular vibrational redistribution and dissociation. The experimental branching ratio and RRKM (Rice-Ramsperger-Kassel-Marcus) calculations favor the formation of C3H3 + C2H2 over the H-atom loss channel. The RRKM calculations also support the observation of ethynylallene as the dominant C5H4 product isomer.

Photodissociation dynamics of the simplest alkyl peroxy radicals, CH3OO and C2H5OO, at 248 nm.

The photodissociation dynamics of the simplest alkyl peroxy radicals, methyl peroxy (CH3OO) and ethyl peroxy (C2H5OO), are investigated using fast beam photofragment translational spectroscopy. A fast beam of CH3OO- or C2H5OO- anions is photodetached to generate neutral radicals that are subsequently dissociated using 248 nm photons. The coincident detection of the photofragment positions and arrival times allows for the determination of mass, translational energy, and angular distributions for both two-body and three-body dissociation events. CH3OO exhibits repulsive O loss resulting in the formation of O(1D) + CH3O with high translational energy release. Minor two-body channels leading to OH + CH2O and CH3O + O(3P) formation are also detected. In addition, small amounts of H + O(3P) + CH2O are observed and attributed to O loss followed by CH3O dissociation. C2H5OO exhibits more complex dissociation dynamics, in which O loss and OH loss occur in roughly equivalent amounts with O(1D) formed as the dominant O atom electronic state via dissociation on a repulsive surface. Minor two-body channels leading to the formation of O2 + C2H5 and HO2 + C2H4 are also observed and attributed to a ground state dissociation pathway following internal conversion. Additionally, C2H5OO dissociation yields a three-body product channel, CH3 + O(3P) + CH2O, for which the proposed mechanism is repulsive O loss followed by the dissociation of C2H5O over a barrier. These results are compared to a recent study of tert-butyl peroxy (t-BuOO) in which 248 nm excitation results in three-body dissociation and ground state two-body dissociation but no O(1D) production.

A measurement of the photoionization cross section of CH2Cl via photofragment translational spectroscopy of dichloromethane

We characterize the 157nm photodissociation of dichloromethane (CH2Cl2) using photofragment translational spectroscopy, detecting the products with photoionization mass spectrometry. The major photodissociation products are Cl+CH2Cl and HCl+CHCl. Comparing the integrated ion signal at m/e=35 (Cl+) and m/e=49 (CH2Cl+) gives the partial photoionization cross section of CH2Cl to parent ion to be σ=26.6Mb at 13.7eV. This value is a quantitative anchor point of the energy-dependent photoionization cross section. In recent work we used this result to quantify the product branching to HCO+CH2Cl in the photodissociation of 2-chloroacetaldehyde.

The collision-free photochemistry of methyl azide at 157 nm: Mechanism and energy release.

Synchrotron radiation VUV-photoionization based photofragment translational spectroscopy was used to identify the primary and secondary photodissociation reactions of methyl azide (CH3N3) at 157 nm under collision-free conditions. Two primary dissociation channels are identified, leading to CH3 + N3 (the radical channel) and CH3N + N2 (the molecular elimination channel). The last channel is the major dissociation pathway, but unlike work at longer photolysis wavelengths, here, the radical channel exclusively produces the higher energy isomer cyclic-N3. Product time-of-flight data for both channels were obtained and compared with earlier work on methyl azide photochemistry at 193 nm based on electron impact ionization, allowing us to estimate a product branching ratio ΦCH3-N3 ΦCH3N-N2 =2.3%±0.6%97.7%±0.6%.

Photofragmentation dynamics of N,N-dimethylformamide following excitation at 193 nm.

N,N-dimethylformamide, HCON(CH3)2, is a useful model compound for investigating the peptide bond photofragmentation dynamics. We report data from a comprehensive experimental and theoretical study into the photofragmentation dynamics of N,N-dimethylformamide in the gas phase at 193 nm. Through a combination of velocity-map imaging and hydrogen atom Rydberg tagging photofragment translational spectroscopy we have identified two primary fragmentation channels, namely, fission of the N-CO "peptide" bond and N-CH3 bond fission leading to the loss of CH3. The possible fragmentation channels leading to the observed products are rationalised with recourse to CASPT2 calculations of the ground and first few excited-state potential energy curves along the relevant dissociation coordinates, and the results are compared with the data from previous experimental and theoretical studies on the same system.