Solid Parahydrogen Research Articles

Electronic Spectroscopy of Ovalene: Reassignment of the S2(B3u)- S0(Ag) Transition.

As part of our experiments to characterize solid para-hydrogen (para-H2) as a matrix host for electronic spectroscopy with potential applications in the ongoing quest for the carriers of the diffuse interstellar bands (DIB), we studied dispersed fluorescence and fluorescence excitation spectra of ovalene (C32H14), a planar polycyclic aromatic hydrocarbon (PAH) of D2h symmetry. Although generally in good agreement with previously reported data for jet-cooled C32H14, our results, in conjunction with quantum-chemical calculations, indicate that the observed spectral progressions are associated with the S2(B3u)-S0(Ag) electronic transition instead of the originally assigned S1-S0 transition for C32H14 in a supersonic jet, and that the previously reported origin band was misassigned and should be located at ∼21050 cm-1. The reassignment is further supported by the comparably long fluorescence lifetime of ∼1.7 μs. From an analysis of spectral features located >1600 cm-1 in the fluorescence excitation spectrum, we estimate an S2(B3u)-S3(B1g) energy gap of ∼350 cm-1.

Identification of HOC•HC(O)H, HOCH2C•O, and HOCH2CH2O• Intermediates in the Reaction of H + Glycolaldehyde in Solid Para-Hydrogen and Its Implication to the Interstellar Formation of Complex Sugars.

Glycolaldehyde [HOCH2C(O)H, GA], the primitive sugar-like molecule detected in the interstellar medium (ISM), is a potential precursor for the synthesis of complex sugars. Despite its importance, the mechanism governing the formation of these higher-order sugars from GA under interstellar circumstances remains elusive. Radical intermediates HOCH2CH2O• (1), HOCH2C•HOH (2), HOCH2C•O (3), HOC•HC(O)H (4), and O•CH2C(O)H (5) derived from GA could be potential precursors for the formation of glyceraldehyde (aldose sugar), dihydroxyacetone (ketose sugar), and ethylene glycol (sugar alcohol) in dark regions of ISM. However, the spectral identification of these intermediates and their roles were little investigated. We conducted reactions involving H atoms and the Cis-cis conformer of GA (Cc-GA) in solid p-H2 at 3.2 K and identified IR spectra of radicals Cc-HOCH2C•O (3) and Cc-HOC•HC(O)H (4) produced from H abstraction as well as closed-shell HOCHCO (6) produced via consecutive H abstraction of GA. In addition, Cc-HOCH2CH2O• (1) and C•H2OH + H2CO (7) were produced through the H addition and the H-induced fragmentation channels, respectively. In darkness, when only H-tunneling reactions occurred, the formation of (3) was major and that of (1) was minor. In contrast, during IR irradiation to produce H atoms with higher energy, the formation of (4) and C•H2OH + H2CO (7) became important. We also successfully converted most Cc-GA to the second-lowest-energy conformer Trans-trans-GA (Tt-GA) by prolonged IR irradiation at 2827 nm to investigate H + Tt-GA; Tt-HOCH2C•O (3'), Tt-HOC•HC(O)H (4'), HOCHCO (6), Tt-HOCH2CH2O• (1'), and C•H2OH + H2CO (7) were observed. We discuss possible routes for the formation of higher-order sugars or related compounds involving (7), (1), (3), and (4), but neither (2), which was proposed previously, nor (5) plays a significant role in H + GA. Such previously unreported rich chemistry in the reaction of H + GA, with four channels of three distinct types, indicates the multiple roles that GA might play in astronomical chemistry.

A platform for planar dynamic compression of crystalline hydrogen toward the terapascal regime

We describe a method for laser-driven planar compression of crystalline hydrogen that starts with a sample of solid para-hydrogen (even-valued rotational quantum number j) having an entropy of 0.06 kB/molecule at 10 K and 2 atm, with Boltzmann constant kB. Starting with this low-entropy state, the sample is compressed using a small initial shock (<0.2 GPa), followed by a pressure ramp that approaches isentropic loading as the sample is taken to hundreds of GPa. Planar loading allows for quantitative compression measurements; the objective of our low-entropy compression is to keep the sample cold enough to characterize crystalline hydrogen toward the terapascal range.

Fluorescence Excitation and Dispersed Fluorescence Spectra of the First Electronic Excited (S1) State of peri-Hexabenzocoronene (C42H18) Isolated in Solid para-Hydrogen.

Large polycyclic aromatic hydrocarbons (PAH) and their cationic, hydrogenated, and protonated derivatives have long been considered as promising candidates for the carriers of the diffuse interstellar bands. peri-Hexabenzocoronene (peri-HBC, C42H18) is a large, compact PAH, and, to the best of our knowledge, the largest centrosymmetric all-benzenoid PAH for which electronic spectroscopy data has been published. In this work, we present the dispersed fluorescence and fluorescence excitation spectra of the first electronic excited (S1) state of peri-HBC isolated in solid para-H2 and provide the first detailed vibronic analysis of observed features. The observed spectra agree with the emission and absorption spectra simulated according to optimized geometries and scaled harmonic vibrational frequencies calculated at the density functional theory (DFT) level using a Franck-Condon Herzberg-Teller approach; the spectral bands are associated solely with vibrational normal modes of approximate e2g symmetry and their combinations with vibrational modes of approximately a1g symmetry. We clearly observed the position of the S1-S0 electronic transition origin of peri-HBC at 22,088 cm-1 (452.7 nm), which was unreported previously. The matrix shift of ∼110 cm-1 to the red relative to the gas-phase value was estimated by comparison of two reported gas-phase bands with our work. Because of the significant deviation from the reported wavelengths of DIB, the weakness of the S1-S0 electronic transitions, and the lack of reported DIB at <400 nm where the intense S4 ← S0 band of peri-HBC is located, peri-HBC is unlikely to contribute to DIB.

Electron thermalization length in solid para-hydrogen at low-temperature.

We report the first ever measurements of the thermalization length of low-energy electrons injected into solid para-hydrogen at a temperature T ≈ 2.8 K. The use of the pulsed Townsend photoinjection technique has allowed us to investigate the behavior of quasi-free electrons rather than of massive, slow negative charges, as reported in all previous literature. We have found an average thermalization length ⟨z0⟩ = 26.1 nm, which is three to five times longer than that in liquid helium at the same temperature.

Conformational analysis of simple oxygenated hydrocarbons in a solid parahydrogen matrix

Acetone, acetaldehyde, propylene oxide, propionaldehyde, and 2-propanol are all simple oxygen-containing organic molecules, and play an important role in combustion chemistry, atmospheric chemistry, and astrochemistry. These small molecules are often produced by chemical reactions or UV photolysis of larger molecules containing oxygen atoms. Thus, knowing the IR spectrum of these molecules is important for the identification of (photo)chemical processes of various molecules. In this study, the IR spectra of these five common organic molecules were studied using parahydrogen (pH2) matrix isolation with Fourier transform infrared spectroscopy. Conformational analysis of the IR spectra revealed two conformers of propionaldehyde and 2-propanol exist in the pH2 matrix at 3.8 K. This work will be useful for the identification of products in future pH2 photochemistry experiments.

Infrared Spectra of (Z)- and (E)-•CH2C(CH3)CHI Radicals Produced upon Photodissociation of (Z)- and (E)-(CH2I)(CH3)C═CHI in Solid para-Hydrogen.

Ozonolysis of isoprene is important in atmospheric chemistry because of the abundant emission of isoprene. This process produces the Criegee intermediates CH2OO, methyl vinyl ketone oxide (MVKO, C2H3C(CH3)OO), and methacrolein oxide (MACRO, CH2C(CH3)CHOO). Gaseous MACRO was recently produced and identified in laboratories after photolysis of a mixture of 1,3-diiodo-2-methyl-prop-1-ene [(CH2I)(CH3)C═CHI] and O2, but the conformation-dependent formation mechanism remains unexplored. We report conformation-distinct IR spectra of (E)- and (Z)-(CH2I)(CH3)C═CHI isolated in solid p-H2. Upon irradiation near 300 nm of (E)- and (Z)-(CH2I)(CH3)C═CHI in solid p-H2 at 3.3 K, 3-iodo-2-methyl-prop-1-en-3-yl [•CH2C(CH3)CHI] radicals were characterized, with intense infrared absorption lines at 2991.3, 1458.7, 1434.7, 1317.4, 1190.4, 786.3, 677.9, and 467.2 cm-1 and additional 11 weaker ones assigned to (E)-•CH2C(CH3)CHI and intense lines at 3108.5, 3076.2, 3028.5, 2970.0, 1174.2, 796.0, 683.6, and 609.5 cm-1 and additional 7 weaker ones to (Z)-•CH2C(CH3)CHI. The assignments were derived according to the behaviors of secondary photolysis at 495 and 460 nm and a comparison of the vibrational wavenumbers and IR intensities of the observed lines with those calculated with the B2PLYP-D3/aug-cc-pVTZ-pp method. These observations confirm that only the allylic C-I bond, not the vinylic one, was photodissociated at 290 nm, and in solid p-H2, the excess energy upon photolysis induced no conformational change. When O2 was present in the matrix, several intense lines at 1147.5, 1025.7, 914.4, and 728.7 cm-1, and 4 weaker ones were tentatively assigned to the adduct CH2C(CH3)CHIOO; the assignments were supported by 18O2 isotopic experiments. Unlike in the gaseous phase, the remaining C-I bond of this adduct could not break to form MACRO because of the efficient quenching in a low-temperature matrix.

Infrared Spectroscopic Studies of Oxygen Atom Quantum Diffusion in Solid Parahydrogen.

The thermally induced diffusion of atomic species in noble gas matrices was studied extensively in the 1990s to investigate low-temperature solid-state reactions and to synthesize reactive intermediates. In contrast, much less is known about the diffusion of atomic species in quantum solids such as solid parahydrogen (p-H2). While hydrogen atoms were shown to diffuse in normal-hydrogen solids at 4.2 K as early as 1989, the diffusion of other atomic species in solid p-H2 has not been reported in the literature. The in situ photogeneration of atomic oxygen, by ArF laser irradiation of an O2-doped p-H2 solid at 193 nm, is studied here to investigate the diffusion of O(3P) atoms in a quantum solid. The O(3P) atom mobility is detected by measuring the kinetics of the O(3P) + O2 → O3 reaction after photolysis via infrared spectroscopy of the O3 reaction product. This reaction is barrierless and is thus assumed to be diffusion-controlled under these conditions such that the reaction rate constant can be used to estimate the oxygen atom diffusion coefficient. The O3 growth curves are well fit by single exponential expressions allowing the pseudo-first-order rate constant for the O(3P) + O2 → O3 reaction to be extracted. The reaction rates are affected strongly by the p-H2 crystal morphology and display a non-Arrhenius-type temperature dependence consistent with quantum diffusion of the O(3P) atom. The experimental results are compared to H(2S) atom reaction studies in p-H2, analogous studies in noble gas matrices, and laboratory studies of atomic diffusion in astronomical ices and surfaces.

Equation of state of solid parahydrogen using ab initio two-body and three-body interaction potentials.

We present the equation of state of solid parahydrogen between 0.024 and 0.1Å-3 at T = 4.2 K, calculated using path integral Monte Carlo simulations, with ab initio two-body and three-body interaction potentials. We correct for finite size simulation errors using potential tail corrections. Trotter factorization errors are accounted for either via extrapolation or by using a suitably small imaginary time step. We incorporate the three-body interaction using two methods: (1) the full inclusion method, where pair and three-body interactions are used in both Monte Carlo sampling and in the energy estimators, and (2) the perturbative method, where three-body interactions are omitted from sampling but are still present in energy estimations. Both treatments of the three-body interaction return very similar total energies and pressures. The presence of three-body interactions has only minor effects on the structural properties of the solid. Whereas the pair interaction, on its own, significantly overestimates the pressure of solid parahydrogen, the additional presence of the three-body interaction causes a severe underestimation of the pressure. Our findings suggest that accurate simulations of solid parahydrogen require four-body and possibly higher-order many-body interactions. It may also be the case that static interaction potentials are entirely unsuitable for simulations of solid parahydrogen at high densities.

Infrared and Laser-Induced Fluorescence Spectra of Sumanene Isolated in Solid para-Hydrogen.

The para-hydrogen (p-H2) matrix-isolation technique has been scarcely used to record electronic absorption and emission spectra. It is expected that its small matrix shifts due to diminished molecular interactions and the softness of the lattice might be advantageous to help identify the carriers of the diffuse interstellar bands. In this article, we present infrared, fluorescence excitation, and dispersed fluorescence spectra of sumanene (C21H12), a bowl-shaped polycyclic aromatic hydrocarbon and a fragment of C60, isolated in solid p-H2. The recorded vibrational wavenumbers from infrared and dispersed fluorescence agree with the scaled harmonic vibrational wavenumbers calculated with the B3PW91/6-311++G(2d,2p) and B3LYP/6-311++G(2d,2p) methods. The recorded fluorescence excitation spectra are consistent with the spectra of jet-cooled gas-phase C21H12 reported previously by Kunishige et al. We found a rather small matrix shift of 55 cm-1 for the S1-S0 electronic transition origin located at 27 888 cm-1. Vibrational wavenumbers associated with the S1 state of C21H12 inferred from the experimental spectrum can be assigned mostly to fundamental normal modes; they are in satisfactory agreement with scaled harmonic vibrational wavenumbers calculated at the TD-B3PW91/6-311++G(2d,2p) level of theory. Significantly more vibrational modes of the S1 state were identified as compared with those in the reported gas-phase work. The potential of p-H2 matrix-isolation spectroscopy to provide electronic excitation spectra suitable for comparison to astronomical observations is discussed by comparing the spectra of C21H12 isolated in solid p-H2 and in solid Ne, a matrix host commonly employed in astrochemistry.

Hydrogen-Atom-Assisted Uphill Isomerization of N-Methylformamide in Darkness.

N-Methylformamide, HC(O)NH(CH3), is the smallest amide detected in the interstellar medium that can exist as cis and trans isomers. We performed reactions of H atoms with trans-NMF in solid para-hydrogen at 3.3 K and found that the cis-NMF isomer, which has higher energy, increased continuously in darkness, demonstrating a previously overlooked and seemingly unlikely isomerization of prebiotic molecules through H-atom tunneling reactions in the absence of light. Infrared spectra of radical intermediates trans-•C(O)NH(CH3) and trans-HC(O)NH(•CH2) were identified. Further H addition and H abstraction enhanced the formation of CH3NCO, HNCO, and CH2NH in the H-rich experiments. These results indicate that, unlike the dual cycle of H-abstraction and H-addition channels chemically linking formamide and HNCO, the H addition to CH3NCO produced only cis-radicals that led to cis-NMF. Furthermore, H-atom-induced fragmentation by breaking the C-C bond provides links between NMF and HCNO/CH2NH. These endothermic isomerization/decomposition reactions become possible through the coupling with H + H → H2.

High-purity solid parahydrogen.

Alkali atoms trapped in solid hydrogen matrices have demonstrated ultralong electron spin coherence times and are promising as quantum sensors. Their spin coherence is limited by magnetic noise from naturally occurring orthohydrogen molecules in the parahydrogen matrix. In the gas phase, the orthohydrogen component of hydrogen can be converted to parahydrogen by flowing it over a catalyst held at cryogenic temperatures, with lower temperatures giving a lower orthohydrogen fraction. In this work, we use a single cryostat to reduce the orthohydrogen fraction of hydrogen gas and grow a solid matrix from the resulting high-purity parahydrogen. We demonstrate the operation of the catalyst down to a temperature of 8K, and we spectroscopically verify that orthohydrogen impurities in the resulting solid are at a level <10-6. We also find that, at sufficiently low temperatures, the cryogenic catalyst provides isotopic purification, reducing the HD fraction.

Radiative properties of rubidium atoms trapped in solid neon and parahydrogen

It is known from ensemble measurements that rubidium atoms trapped in solid parahydrogen have favorable properties for quantum sensing of magnetic fields. To use a single rubidium atom as a quantum sensor requires a technique capable of efficiently measuring the internal state of a single atom, such as laser-induced fluorescence. In this work we search for laser-induced fluorescence from ensembles of rubidium atoms trapped in solid parahydrogen and, separately, in solid neon. In parahydrogen we find no evidence of fluorescence over the range explored, and place upper limits on the radiative branching ratio. In neon, we observe laser induced fluorescence, measure the spectrum of the emitted light, and measure the excited state lifetime in the matrix. Bleaching of atoms from the excitation light is also reported.

High resolution infrared spectroscopy of (HCl)2 and (DCl)2 isolated in solid parahydrogen: Interchange-tunneling in a quantum solid.

Infrared spectroscopic studies of weakly bound clusters isolated in solid parahydrogen (pH2) that exhibit large-amplitude tunneling motions are needed to probe how quantum solvation perturbs these types of coherent dynamics. We report high resolution Fourier transform infrared absorption spectra of (HCl)2, HCl-DCl, and (DCl)2 isolated in solid pH2 in the 2.4-4.8 K temperature range. The (HCl)2 spectra show a remarkable amount of fine structures that can be rigorously assigned to vibration-rotation-tunneling transitions of (HCl)2 trapped in double substitution sites in the pH2 matrix where end-over-end rotation of the cluster is quenched. The spectra are assigned using a combination of isotopically (H/D and 35Cl/37Cl) enriched samples, polarized IR absorption measurements, and four-line combination differences. The interchange-tunneling (IT) splitting in the ground vibrational state for in-plane and out-of-plane H35Cl-H37Cl dimers is 6.026(1) and 6.950(1) cm-1, respectively, which are factors of 2.565 and 2.224 smaller than in the gas phase dimer. In contrast, the (DCl)2 results show larger perturbations where the ground vibrational state IT splitting in D35Cl-D37Cl is 1.141(1) cm-1, which is a factor of 5.223 smaller than in the gas phase, and the tunneling motion is quenched in excited intramolecular vibrational states. The results are compared to similar measurements on (HCl)2 made in liquid helium nanodroplets to illustrate the similarities and differences in how both these quantum solvents interact with large amplitude tunneling motions of an embedded chromophore.

Matrix isolation spectroscopy and conformational analysis of epichlorohydrin in solid parahydrogen

Fundamental vibrational modes of epichlorohydrin have been characterized in a solid parahydrogen matrix at 4.3 K using FTIR spectroscopy. All three stable conformations of epichlorohydrin, gauche-I, gauche-II and cis, were identified in the infrared spectra. The effect of chlorine isotopic substitution was also observed in the ν19 and ν20 vibrational modes, which correspond to the C-C-Cl bending and C-Cl stretching motions, respectively. The relative populations of three conformers of this molecule in parahydrogen have been experimentally determined from three well-separated fundamental modes (ν7,ν16 and ν18), and compared with Boltzmann populations derived from quantum chemical calculations at various temperatures. The analysis suggests that relative conformer population ratio of gauche-I:gauche-II:cis is ~65%:~24%:~11% in solid parahydrogen at 4 K. This population agrees well with the equilibrium Boltzmann distribution at room temperature, which indicates that the conformational population is preserved during the cooling process in which the epichlorohydrin molecules are trapped in solid parahydrogen.

Hydrogen atom quantum diffusion in solid parahydrogen: The H + N2O → cis-HNNO → trans-HNNO reaction.

The diffusion and reactivity of hydrogen atoms in solid parahydrogen at temperatures between 1.5 K and 4.3 K are investigated by high-resolution infrared spectroscopy. Hydrogen atoms are produced within solid parahydrogen as the by-products of the 193 nm in situ photolysis of N2O, which induces a two-step tunneling reaction, H + N2O → cis-HNNO → trans-HNNO. The second-order rate constant for the first step to form cis-HNNO is found to be inversely proportional to the N2O concentration after photolysis, indicating that the hydrogen atoms move through solid parahydrogen via quantum diffusion. This reaction only readily occurs at temperatures below 2.8 K, not due to an increased rate constant for the first reaction step at low temperatures but rather due to an increased selectivity to the reaction. The rate constant for the second step of the reaction mechanism involving unimolecular isomerization is shown to be independent of the N2O concentration as expected. The inverse concentration dependence of the rate constant for the reaction step that involves the hydrogen atom demonstrates clearly that quantum diffusion influences the reactivity of the hydrogen atoms in solid parahydrogen, which does not have an analogy in classical reaction kinetics.

Hydrogenation of pyrrole: Infrared spectra of the 2,3-dihydropyrrol-2-yl and 2,3-dihydropyrrol-3-yl radicals isolated in solid para-hydrogen.

The reaction of hydrogen atoms (H) with pyrrole (C4H4NH) in solid para-hydrogen (p-H2) matrices at 3.2 K has been studied by infrared spectroscopy. Upon reaction of the H atoms with pyrrole in p-H2, a new series of lines appeared in the infrared spectrum, and based on secondary photolysis, it was determined that the majority of the new lines belong to two distinct chemical species; these lines are designated as set A and set B. According to quantum-chemical calculations performed at the B3PW91/6-311++G(2d,2p) level, the most likely reactions to occur under low temperature conditions in solid p-H2 are the addition of an H atom to carbon 2 or 3 of C4H4NH to produce the corresponding hydrogen-atom addition radicals (HC4H4NH•). When the lines in sets A and B are compared to the scaled harmonic and anharmonic vibrational infrared stick spectra of these two radicals, the best agreement for set A is with the radical produced by the addition to carbon 3 (2,3-dihydropyrrol-2-yl radical, 3-HC4H4NH•), and the best agreement for set B is with the radical produced by addition to carbon 2 (2,3-dihydropyrrol-3-yl radical, 2-HC4H4NH•). The ratio of the 2-HC4H4NH• to 3-HC4H4NH• radicals is estimated to be 4-5:1, consistent with the smaller predicted barrier height for the H-atom addition to C2. In addition to the assignments of the 2,3-dihydropyrrol-2-yl and 2,3-dihydropyrrol-3-yl radicals, a series of lines that appear upon 455-nm photolysis have been assigned to 1,3-pyrrolenine (2-HC4H4N).

Infrared spectroscopy of H+(CO)2 in the gas phase and in para-hydrogen matrices.

The H+(CO)2 and D+(CO)2 molecular ions were investigated by infrared spectroscopy in the gas phase and in para-hydrogen matrices. In the gas phase, ions were generated in a supersonic molecular beam by a pulsed electrical discharge. After extraction into a time-of-flight mass spectrometer, the ions were mass selected and probed by infrared laser photodissociation spectroscopy in the 700 cm-1-3500 cm-1 region. Spectra were measured using either argon or neon tagging, as well as tagging with an excess CO molecule. In solid para-hydrogen, ions were generated by electron bombardment of a mixture of CO and hydrogen, and absorption spectra were recorded in the 400 cm-1-4000 cm-1 region with a Fourier-transform infrared spectrometer. A comparison of the measured spectra with the predictions of anharmonic theory at the CCSD(T)/ANO1 level suggests that the predominant isomers formed by either argon tagging or para-hydrogen isolation are higher lying (+7.8 kcal mol-1), less symmetric isomers, and not the global minimum proton-bound dimer. Changing the formation environment or tagging strategy produces other non-centrosymmetric structures, but there is no spectroscopic evidence for the centrosymmetric proton-bound dimer. The formation of higher energy isomers may be caused by a kinetic effect, such as the binding of X (=Ar, Ne, or H2) to H+(CO) prior to the formation of X H+(CO)2. Regardless, there is a strong tendency to produce non-centrosymmetric structures in which HCO+ remains an intact core ion.

Infrared Spectra of Monohydrogenated Aniline, ortho- and para-HC6H5NH2, Generated in Solid para-Hydrogen.

The isomers of monohydrogenated aniline (HC6H5NH2) are regarded as important intermediates in reduction reactions of aniline, but their spectral identification has been limited to electron paramagnetic resonance in an adamantane matrix. We report here infrared (IR) spectra of two least-energy isomers of HC6H5NH2, produced on electron bombardment during the deposition of a matrix of aniline and para-hydrogen at 3.2 K. The intensities of IR lines of HC6H5NH2 increased during maintenance of the electron-bombarded matrix in darkness for a prolonged period because of the neutralization of protonated aniline, H+C6H5NH2, by trapped electrons and further reactions between aniline and the unreacted hydrogen atoms that were produced during electron bombardment. The observed lines were grouped according to their behaviors on secondary photolysis with light at 520, 465, and 375 nm. On comparison of experimental spectra with quantum chemically predicted spectra for four possible isomers of HC6H5NH2, lines in one group were assigned to the most stable ortho-HC6H5NH2 and those in the other group were assigned to the secondmost stable para-HC6H5NH2. Their photolytic behaviors at varied wavelengths are consistent with predicted ultraviolet absorption bands. The mechanisms of formation of these isomers are discussed according to semiquantitative analysis.

UV photochemistry of 1,3-cyclohexadiene isolated in solid parahydrogen

1,3-cyclohexadiene was isolated in solid parahydrogen, and its photochemical reactions were studied via irradiation with 193 nm photons from an ArF excimer laser. Photoproducts were identified using Fourier-transform infrared spectroscopy supported by density functional theory calculations. Photolysis with 193 nm light caused the formation of two well-characterized conformers of 1,3,5-hexatriene, tZt-1,3,5-hexatriene and tEt-1,3,5-hexatriene. A third initial photoproduct was identified as the conformer cZc-1,3,5-hexatriene, and its infrared spectrum was characterized for the first time. In addition, the bicyclo[2.2.0]hex‑2-ene and 1-methyl-bicyclo[2.1.0]pent‑2-ene were also found to be a minor products from photo-induced ring-closure reactions, where the latter further converts to 2-methyl-cyclopentadiene. The reaction mechanisms and stability of these products are discussed using infrared spectroscopy and density functional theory calculations.