Dissociation Channels Research Articles

Valence Photoionization and Energetics of Vanillin, a Sustainable Feedstock Candidate.

We studied the valence photoionization of vanillin by photoelectron photoion coincidence spectroscopy in the 8.20-19.80 eV photon energy range. Vertical ionization energies by EOM-IP-CCSD calculations reproduce the photoelectron spectral features. Composite method calculations and Franck-Condon simulation of the weak, ground-state band yield the adiabatic ionization energy of the most stable vanillin conformer as 8.306(20) eV. The lowest energy dissociative photoionization channels correspond to hydrogen atom, carbon monoxide, and methyl losses, which form the dominant C8H7O3+ (m/z 151) and the less intense C7H8O2+ (m/z 124) and C7H5O3+ (m/z 137) fragment ions in parallel dissociation channels at modeled 0 K appearance energies of 10.13(1), 10.40(3), and 10.58(10) eV, respectively. On the basis of the breakdown diagram, we explore the energetics of sequential methyl and carbon monoxide loss channels, which dominate the fragmentation mechanism at higher photon energies. The 0 K appearance energy for sequential CO loss from the m/z 151 fragment to C7H7O2+ (m/z 123) is 12.99(10) eV, and for sequential CH3 loss from the m/z 123 fragment to C6H4O2+ (m/z 108), it is 15.40(20) eV based on the model. Finally, we review the thermochemistry of the bi- and trifunctionalized benzene derivatives guaiacol, hydroxybenzaldehyde, anisaldehyde, and vanillin. On the basis of isodesmic functional group exchange reactions, we propose new enthalpies of formations, among them ΔfH°298K(vanillin, g) = -383.5 ± 2.9 kJ mol-1. These mechanistic insights and ab initio thermochemistry results will support analytical works to study lignin conversion involving vanillin.

Coulomb-explosion imaging of carbon monoxide dimers

We report on experimental results obtained from collisions of slow highly charged Ar9+ ions with a carbon monoxide dimer (CO)2 target. A COLTRIMS setup and a Coulomb explosion imaging approach are used to reconstruct the structure of the CO dimers. The three dimensional structure is deduced from the 2-body and 3-body dissociation channels from which both the intermolecular bond length and the relative orientation of the two molecules are determined. For the 3-body channels, the experimental data are interpreted with the help of a classical model in which the trajectories of the three emitted fragments are numerically integrated. We measured the equilibrium intermolecular distance to be Re = 4.2 A. The orientation of both CO molecules with respect to the dimer axis is found to be quasi-isotropic due to the large vibrational temperature of the gas jet.

Relative Energetics of the Gas Phase Protomers of p-Aminobenzoic Acid and the Effect of Protonation Site on Fragmentation.

Guided ion beam tandem mass spectrometry (GIBMS) is used to investigate the energy-dependent threshold collision-induced dissociation (TCID) of the two protonated isomers (protomers) of p-aminobenzoic acid (p-ABA). The O-protomer of p-ABA (protonated at the carbonyl oxygen) was generated via electrospray ionization (ESI) from a methanol/water solution, whereas the N-protomer (protonated at the amine) was produced via ESI from an acetonitrile/water solution. The two protomers are clearly distinguishable from differences in the onsets of the fragmentation channels and in the abundance and identity of the products observed. Additional GIBMS experiments were performed on protonated benzoic acid (BA) and aniline, which serve as simple models for fragmentation driven by protonation at the carbonyl or amine group of p-ABA and provide insights into the dissociation channels of the two p-ABA protomers. Theoretical calculations were carried out to determine the dissociation mechanisms and for comparison with the experimental thermochemistry, which is obtained from modeling the kinetic energy dependent TCID cross sections after accounting for multiple collisions, kinetic shifts, competition between channels, and sequential dissociations. Calculations together with the energy-resolved experiments show that a product ion (C5H5+, m/z 65) common to both p-ABA protomers is produced from sequential dissociations via two different mechanisms. Furthermore, we demonstrate here that the relative stabilities of the two p-ABA protomers can be determined directly from experiment via shared product channels for which there are no barriers exceeding their asymptotic energies. Our results indicate that the two p-ABA protomers are nearly isoenergetic in the gas phase with a relative energy of 0.01 ± 0.26 eV favoring the O-protomer over the N-protomer. This result is in good agreement with calculations at the MP2 and CCSD(T) levels of theory.

The influence of the methionine residue on the dissociation mechanisms of photoionized methionine-enkephalin probed by VUV action spectroscopy

VUV action spectroscopy has recently gained interest for the study of peptides and proteins. However, numerous aspects of the fundamental processes involved in the photodissociation are yet to be understood. It can, for example, be expected that sulfur-containing amino-acid residues have a significant impact on the dissociation processes following photoionization because of their potential involvement in the transport of electron holes in proteins. In order to investigate the influence of the sulfur-containing methionine residue on the VUV photodissociation of a small peptide a VUV action spectroscopy study of gas-phase protonated methionine-enkephalin and leucine-enkephalin in the photon energy range of 6–35 eV was performed. The results show that upon non-ionizing photoexcitation, the fragmentation patterns of the two peptides are nearly identical, whereas significant differences were observed upon photoionization. The differences between the fragment yields and the identified specific dissociation channels for methionine-enkephalin could be explained by the high electron hole affinity of sulfur, which efficiently directs the radical to the methionine side chain. Additionally, for both peptides the presence of the intact photoionized precursor ions was confirmed by their isotopic patterns and the stability of these species could be evaluated.Graphic abstract

Thymidine and stavudine molecules in reactions with low-energy electrons

The negative ion formation and fragmentation processes in thymidine and stavudine were studied by means of resonant electron capture mass spectrometry in the electron energy range 0–14 eV. Stavudine is a nucleoside analog of thymidine, that differs from the latter by the presence of double bond in the deoxyribose moiety. In the energy range below 5 eV transient negative ions have been found to arise via shape resonances resulting in electron attachment into the empty π*-orbitals. The main fragmentation channels for molecular ions are the H-atom loss and N-glycosidic bond cleavage between sugar and a nucleobase moieties. The dissociative electron attachment cross sections for the fragment negative ions were measured. The structures for some observed anions and neutral counterparts were suggested basing on the thermochemical approach for dissociative reactions energy balance under the support of quantum chemical calculations. The processes of ion formation in thymidine were found to be similar to those revealed previously for deoxyuridine nucleoside. In contrast, very strong dissociative channel was found for stavudine yielding [M–R]– ions (where R is a sugar moiety) in the energy range <3 eV. The efficient fragmentation found for stavudine in the low energy electron attachment reactions may have implications for the design of nucleoside radiosensitizers for cancer therapy.

Fragmentation of isocyanic acid, HNCO, following core excitation and ionization.

We report a study on the fragmentation of core-ionized and core-excited isocyanic acid, HNCO, using Auger-electron/photoion coincidence spectroscopy. Site-selectivity is observed both for normal and resonant Auger electron decay. Oxygen 1s ionization leads to the CO+ + NH+ ion pairs, while nitrogen 1s ionization results in three-body dissociation and an efficient fragmentation of the H-N bond in the dication. Upon 1s → 10a' resonant excitation, clear differences between O and N sites are discernible as well. In both cases, the correlation between the dissociation channel and the binding energy of the normal Auger electrons indicates that the fragmentation pattern is governed by the excess energy available in the final ionic state. High-level multireference calculations suggest pathways to the formation of the fragment ions NO+ and HCO+, which are observed although the parent compound contains neither N-O nor H-C bonds. This work contributes to the goal to achieve and understand site-selective fragmentation upon ionization and excitation of molecules with soft x-ray radiation.

Role of the Environment in Quenching the Production of H_{3}^{+} from Dicationic Clusters of Methanol.

Ionization and subsequent isomerization of organic molecules has been suggested as an important source of trihydrogen H_{3}^{+} cations in outer space. The high interest in such reactions has initiated many experimental and theoretical studies for various molecules. Here, we report measurements as well as abinitio molecular dynamics simulations on the fragmentation of dicationic methanol monomers and clusters ionized by low-energy (90eV) electrons. Experimentally, for dicationic monomers, a fragmentation channel for the formation of H_{3}^{+} in coincidence with a COH^{+} cation is observed. The simulations show that an intermediate neutral H_{2} is formed in the first step, and its roaming around the dication ends in the formation of H_{3}^{+}. The entire reaction takes about 100-500fs. The calculated kinetic energy release for the H_{3}^{+}+COH^{+} ion pair is in excellent agreement with the experimental result. In contrast, for the dicationic clusters, due to the possibility of distributing the two charges onto different molecules, several fast dissociation channels occur and suppress the roaming of H_{2} and formation of H_{3}^{+}. The present Letter suggests that the quenching of H_{3}^{+} formation by the chemical environment is a general phenomenon in dicationic clusters of organic molecules.

Theoretical prediction of an NXeH4+ ion with N-Xe triple bond

The NXeH4+ ion containing N-Xe triple bond is investigated by using DFT and ab inito calculations. The predicted value of N-Xe bond length (1.813 Å calculated by MP2) is slightly larger than that of the standard N-Xe triple bond (1.76 Å, i.e. the sum of double radii of N and Xe). Two different dissociation channels have been found to further investigate the stability of NXeH4+ ion. Molecular orbital (MO) analysis implies there are a σ-bond and two π-bonds between N and Xe atoms in NXeH4+ species. The N-Xe triple bond is further explored by the electron density distribution (EDD), and the electron localization function (ELF) approaches.

Photodissociation branching ratios of12C16O from 110 500 to 113 045 cm−1: first observation of the C(1S) channel

Carbon monoxide (CO) is one of the most abundant molecular species in comets. Its photodissociation by the solar radiation in the vacuum ultraviolet (VUV) region produces excited atomic fragments C(1D), C(1S), and O(1D), which radiate at characteristic wavelengths when they decay to lower states. The fractional rate constants for generating these fragments from CO photodissociation under the entire range of the solar radiation field are key input values in modelling the observed atomic emission intensities from comets. In this study, the branching ratios of the four lowest dissociation channels C(3P)+O(3P), C(1D)+O(3P), C(3P)+O(1D), and C(1S)+O(3P) of the12C16O photodissociation are measured in the VUV energy range between the threshold of producing the C(1S)+O(3P) channel (~110 500 cm−1) and the ionisation energy (IE) of12C16O (~113 045 cm−1). We measured these ratios using the VUV time-slice velocity-map ion imaging apparatus. We observe a number of high Rydberg states in the aforementioned energy range, with most of them mainly producing ground C(3P) and O(3P) atomic fragments, and only a few of them producing a significant amount of excited C(1D) or O(1D) fragments. We also observe the excited C(1S) fragment from CO photodissociation and measured its branching ratio for the first time. Based on the photodissociation branching ratios measured in the current and previous studies, we are able to estimate the relative percentages of the excited atomic fragments C(1D), C(1S), and O(1D) from the solar photolysis of12C16O below its IE. We discuss the implications for the photochemical modelling of the CO-dominated comet C/2016 R2 (Pan-STARRS).

H-atom rearrangement in NH3 under ion impact

The rearrangement of H-atoms is studied in the interaction of energetic (50–2000 keV) H+ and Arq+ (q = 1, 8) ions with NH3. The technique of recoil ion momentum spectrometry is used to obtain various dissociation channels involved in these collision events. The variation of the relative yields of the H2+ and H3+ ions is obtained as a function of the interaction strength q/v, where q and v are the charge state and velocity of the projectile. It is observed that the yield of H2+ increases with q/v of the projectile, however, H3+ is observed only at the highest q/v.

Strong Differential Photoion Circular Dichroism in Strong-Field Ionization of Chiral Molecules.

We investigate the differential ionization probability of chiral molecules in the strong-field regime as a function of the helicity of the incident light. To this end, we analyze the fourfold ionization of bromochlorofluoromethane (CHBrClF) with subsequent fragmentation into four charged fragments and different dissociation channels of the singly ionized methyloxirane. By resolving for the molecular orientation, we show that the photoion circular dichroism signal strength is increased by 2 orders of magnitude.

Infrared spectroscopy of CO3 •-(H2O)1,2 and CO4 •-(H2O)1,2.

Hydrated molecular anions are present in the atmosphere. Revealing the structure of the microsolvation is key to understanding their chemical properties. The infrared spectra of CO3 •-(H2O)1,2 and CO4 •-(H2O)1,2 were measured via infrared multiple photon dissociation spectroscopy in both warm and cold environments. Redshifted from the free O-H stretch frequency, broad, structured spectra were observed in the O-H stretching region for all cluster ions, which provide information on the interaction of the hydrogen atoms with the central ion. In the C-O stretching region, the spectra exhibit clear maxima, but dissociation of CO3 •-(H2O)1,2 was surprisingly inefficient. While CO3 •-(H2O)1,2 and CO4 •-(H2O) dissociate via loss of water, CO2 loss is the dominant dissociation channel for CO4 •-(H2O)2. The experimental spectra are compared to calculated spectra within the harmonic approximation and from analysis of molecular dynamics simulations. The simulations support the hypothesis that many isomers contribute to the observed spectrum at finite temperatures. The highly fluxional nature of the clusters is the main reason for the spectral broadening, while water-water hydrogen bonding seems to play a minor role in the doubly hydrated species.

Direct observation of charge separation in an organic light harvesting system by femtosecond time-resolved XPS

The ultrafast dynamics of photon-to-charge conversion in an organic light-harvesting system is studied by femtosecond time-resolved X-ray photoemission spectroscopy (TR-XPS) at the free-electron laser FLASH. This novel experimental technique provides site-specific information about charge separation and enables the monitoring of free charge carrier generation dynamics on their natural timescale, here applied to the model donor-acceptor system CuPc:C60. A previously unobserved channel for exciton dissociation into mobile charge carriers is identified, providing the first direct, real-time characterization of the timescale and efficiency of charge generation from low-energy charge-transfer states in an organic heterojunction. The findings give strong support to the emerging realization that charge separation even from energetically disfavored excitonic states is contributing significantly, indicating new options for light harvesting in organic heterojunctions.

Dissociative Ionization of Molecular CF2Br2 under 800 and 400 nm Intense Femtosecond Laser Fields

The interaction between the CF2Br2 molecule and 800/400 nm intense femtosecond laser fields is investigated by direct current (dc) sliced velocity mapping imaging implementation. By analyzing the kinetic energy release distribution and angular distribution of fragment ions, the dissociation channels along C-Br bond cleavage have been determined. The isotropic structure of the angular distribution for CF2Br+ ions is attributed to the coupling between the excited states. Additionally, a unique elimination channel of CF2Br2+ → CF2 + Br2+ has been observed and identified in the case of 400 nm laser field, in which the two C-Br bonds break asynchronously.

The Role of Low Energy Electrons in Radiobiology and Cancer Treatment

Low energy radiation can be produced by all types of high energy radiation. Studies of low energy particle radiation help us to understand the chemistry induced by high energy radiations. Low energy electrons are capable of chemical selectivity in contrast to high energy electrons due to the large number of open dissociative channels in the former case and their resonant nature. Among different types of radiation, low energy electrons have a higher cross-section to DNA damage and they have an important role in the synergistic effect between radiation and chemotherapy anticancer agents in cancer treatment. Analysis of these combined records helps assign function of cells, identify metabolic and regulatory pathways and suggest targets for diagnostics and therapeutics identify animal models to develop new drugs, among other goals of biomedical interest.

Investigating resonant low-energy electron attachment to formamide: Dynamics of model peptide bond dissociation and other fragmentation channels

We report experimental results on three-dimensional momentum imaging measurements of anions generated via dissociative electron attachment to gaseous formamide. From the momentum images, we analyze the angular and kinetic energy distributions for NH$_2^{-}$, O$^{-}$, and H$^{-}$ fragments and discuss the possible electron attachment and dissociation mechanisms for multiple resonances for two ranges of incident electron energies, from 5.3~eV to 6.8~eV, and from 10.0~eV to 11.5~eV. {\it Ab initio} theoretical results for the angular distributions of the NH$_2^{-}$ anion for $\sim$6~eV incident electrons, when compared with the experimental results, strongly suggest that one of the two resonances producing this fragment is a $^2$A$''$ Feshbach resonance.

Studies of Ultrafast Molecular Dynamics by Femtosecond Extreme Ultraviolet Absorption Spectroscopy

Transient absorption spectroscopy is one of the most widely used experimental techniques for time-resolved studies of ultrafast phenomena. Recent advances in the generation of short-wavelength pulses of ultrashort duration have made transient absorption probing of atomic core level transitions possible. In this Highlight Review, we introduce our recent work on using extreme ultraviolet (XUV) transient absorption spectroscopy to investigate the ultrafast molecular dynamics induced by intense laser fields. While investigations of intense laser-molecule interaction have primarily focused on elucidating electron dynamics, it is important to understand the vibrational dynamics that are triggered by intense laser fields because of their coupling to electron dynamics. Probing the iodine 4d core level, our XUV transient absorption studies of iodoalkanes irradiated by intense laser fields elucidate ultrafast dissociative ionization dynamics and vibrational wave packet dynamics. Time-dependent XUV spectral shifts and global analysis of time-resolved XUV transient absorption spectra can be used to reconstruct C–I dissociation dynamics and identify multiple dissociation channels. In addition, XUV transient absorption spectroscopy also unravels both small- and large-amplitude coherent vibrational motion, whose origin can be identified by analyzing the phase of the oscillatory XUV transition energies. Our studies show that XUV transient absorption spectroscopy is a powerful technique for the study of ultrafast molecular dynamics.

Time resolved detection of the S(1D) product of the UV induced dissociation of CS2.

The products formed following the photodissociation of UV (200 nm) excited CS2 are monitored in a time resolved photoelectron spectroscopy experiment using femtosecond XUV (21.5 eV) photons. By spectrally resolving the electrons, we identify separate photoelectron bands related to the CS2 + hν → S(1D) + CS and CS2 + hν → S(3P) + CS dissociation channels, which show different appearance and rise times. The measurements show that there is no delay in the appearance of the S(1D) product contrary to the results of Horio et al. [J. Chem. Phys. 147, 013932 (2017)]. Analysis of the photoelectron yield associated with the atomic products allows us to obtain a S(3P)/S(1D) branching ratio and the rate constants associated with dissociation and intersystem crossing rather than the effective lifetime observed through the measurement of excited state populations alone.

Coulomb explosion and angular distributions of the fragment ions of highly charged CO in the strong laser field

The CO molecular ionization and Coulomb explosion are systematically investigated utilizing a high-resolution time-of-flight mass spectrometer. It is found that the main dissociation channels of highly charged CO, CO, and CO are (2,1), (2,2), and (3,2) respectively, i.e., the charge-symmetric dissociation channel, and their kinetic energy release keep constant with increasing the laser intensity. We obtain the contribution of different molecular states to the dissociation channel by Gaussian fitting the distribution of the channel’s kinetic energy release. With the laser intensity of W/, the angular distributions of CO(=2,3,4), which exhibit high anisotropy, are generated from these different dissociation channels. According to the present theory, we can qualitatively understand that the anisotropy depends on the molecular orbital profile.

Coincident angle-resolved state-selective photoelectron spectroscopy of acetylene molecules: a candidate system for time-resolved dynamics.

The acetylene-vinylidene system serves as a benchmark for investigations of ultrafast dynamical processes where the coupling of the electronic and nuclear degrees of freedom provides a fertile playground to explore the femto- and sub-femto-second physics with coherent extreme-ultraviolet (EUV) photon sources both on the table-top as well as free-electron lasers. We focus on detailed investigations of this molecular system in the photon energy range 19-40 eV where EUV pulses can probe the dynamics effectively. We employ photoelectron-photoion coincidence (PEPICO) spectroscopy to uncover hitherto unrevealed aspects of this system. In this work, the role of excited states of the C2H2+ cation, the primary photoion, is specifically addressed. From photoelectron energy spectra and angular distributions, the nature of the dissociation and isomerization channels is discerned. Exploiting the 4π-collection geometry of the velocity map imaging spectrometer, we not only probe pathways where the efficiency of photoionization is inherently high but also perform PEPICO spectroscopy on relatively weak channels.