Observation of Renner-Teller and predissociation coupled vibronic intensity borrowing in dissociative electron attachment to OCS.

We use a time-of-flight-based velocity map imaging method to look into the dissociative electron attachment to a linear OCS molecule at electron beam energies ranging from 4.5 to 8.5 eV. The conical time-gated wedge slice imaging method is utilized to extract fragments' slice images, kinetic energy (KE), and angular distributions, which provide a complete kinematic understanding of this experiment on the dissociative electron attachment process. We observe that the formation of S- is relatively higher than the O- product. Three distinct dissociative KE bands of S-/OCS have been observed for the 5.0 and 6.5 eV resonance positions. We notice a prominent rovibrationally coupled bimodality for each KE band in the variation of the most probable KE values. When the electron energy is changed from 5.5 to 6.0 eV, we observed vibronic intensity borrowing in the highest momentum band of S- via the Σ â†’ Π symmetric dipole-forbidden transitions within the 1.5 eV energy gap. Multiple peaks in the angular distributions of S- and their modeling indicate the presence of Renner-Teller vibronic splitting. Using Q-Chem's implemented complex absorbing potential-equation of motion-electron affinity coupled cluster singles and doubles aug-cc-pVDZ+4s3p level of multireference-based electronic structure theory, we confirm the presence of OCS temporary negative ion bending vibrations and Renner-Teller vibronic splittings for the Π symmetric states. Additionally, we notice the presence of a non-radiative predissociation continuum (bringing down the rotational spectrum) and speed-dependent angular anisotropy in the S- fragmentation. Our findings at the resonance of OCS at 6.5 eV closely align with the prediction of vibronic intensity borrowing by Orlandi and Siebrand [J. Chem. Phys. 58, 4513 (1973)].

Dissociative electron attachment to carbon tetrachloride probed by velocity map imaging.

Bond-breaking in CCl4via dissociative electron attachment (DEA) has been studied using a velocity map imaging (VMI) spectrometer. A number of effects related to the dissociation dynamics have been revealed. The near-zero eV s-wave electron attachment, which leads to the production of Cl- anions, is accompanied by a very efficient intramolecular vibrational redistribution. This is manifested by a small fraction of the excess energy being released in the form of the fragments' translation energy. A similar effect is observed for higher-lying electronic resonances with one exception: the resonance centered around 6.2 eV leads to the production of fast Cl2- fragments and their angular distribution is forward peaking. This behavior could not be explained with a single-electronic-state model in the axial recoil approximation and is most probably caused by bending dynamics initiated by a Jahn-Teller distortion of the transient anion. The CCl2- fragment has a reverse backward-peaking angular distribution, suggesting the presence of a long-distance electron hopping mechanism between the fragments.

Fragmentation dynamics and absolute dissociative electron attachment cross sections in the low energy electron collision with ethanol.

Dissociative electron attachment (DEA) to ethanol has been probed to study fragmentation dynamics using Time-of-Flight (ToF) mass spectrometric technique. Several fragment ions, namely, H-, O-, OH-, C2H3O- and C2H5O- have been observed. Extra effort has been made to detect low mass ions (here, H-). Absolute DEA cross sections for the formation of O- and OH- have been measured for the first time using relative flow technique (RFT). The threshold energy of different dissociation channels has been calculated using density functional theory (DFT) method. By combining the experimental and theoretical data, we found evidence of hydrogen migration in the production of O and C2H3O- ions.

Breakdown of dipole Born approximation and the role of Rydberg's predissociation for the electron-induced ion-pair dissociation to oxygen in the presence of background gases.

We study the electron-induced ion-pair dissociation to gas-phase oxygen molecules using a state-of-the-art velocity-map ion-imaging technique. The analysis is entirely based on the conical time-gated wedge-shaped velocity slice images of O-/O2 nascent anionic fragments, and the resulting observations are in favor of Van Brunt et al.'s report [R. J. Van Brunt and L. J. Kieffer, J. Chem. Phys. 60, 3057 (1974)]. A new image reconstruction method, Jacobian over parallel slicing, is introduced to overcome the drawback of ion exaggeration in determining the kinetic energy distribution from the time-gated parallel slicing technique, which offers an alternative approach to the wedge slicing method. Most importantly, the role of the quintet-heavy Rydberg state has been drawn out to the complex ion-pair formalism. The extracted kinetic energy and angular distributions from the wedge slice images reveal a high momentum transfer during the ion-pair dissociation process, which could be the finest rationale to observe the breakdown of dipole Born approximation driven by multipole moment associated with the incident electron beam. Three distinct dissociative momentum bands have been precisely identified for O- dissociation. However, radiationless Rydberg's predissociation continuum (≥15%) has become an inherent character of electron-induced ion-pair dissociation, which could be dealt with using the beyond Born-Oppenheimer treatment. The incoherent sum of Σ and Π symmetric-associated ion-pair final states has been precisely identified by modeling the angular distribution of O-/O2 for each of the kinetic energy bands. A negligibly small amount of forward-backward asymmetry is observed in the angular distribution of O-/O2, which might be explained by the dissociative state-specific quantum coherence mechanism as reported [Krishnakumar et al., Nat. Phys. 14, 149 (2018); Kumar et al., arXiv:2206.15024 (2022)] by Prabhudesai et al.

Dissociative electron attachment dynamics of carbon disulfide and violation of axial recoil approximation near 6 eV resonance.

Complete dissociation dynamics of low-energy electron attachment to carbon disulfide have been studied using the velocity slice imaging (VSI) technique. The ion yields of the different fragment anions produced due to the dissociative electron attachment to carbon disulfide for the 5 to 11 eV incident electron energy range have been collected. Two resonances for S- ions are observed at around 6.2 eV and 7.7 eV, while only one resonance for both the CS- and S2- ions at 6.2 eV is present in this energy range. The kinetic energy and the angular distributions of these fragment negative ions at different incident electron energies around the 6.2 eV resonance have been extracted from the velocity slice images. These experimentally obtained angular distributions of different fragment anions combined with previous theoretical calculations provide a detailed picture of the breakdown of axial recoil approximation and the complete dissociation dynamics involved in this resonance.

Dissociation dynamics in low energy electron attachment to ammonia using velocity slice imaging.

The complete dissociation dynamics of low energy electron attachment to the ammonia molecule has been studied using velocity slice imaging (VSI) spectrometry. One low energy resonant peak around 5.5 eV and a broad resonance around 10.5 eV incident electron energies have been observed. The resonant states mainly dissociate via H- and NH2- fragments, though for the upper resonant state, the signature of NH- fragments is also predicted due to a three-body dissociation process. Kinetic energy and angular distributions of the NH2- fragment anions are measured simultaneously around the two resonances. Based on our experimental observations, we conclude that a temporary negative ion (TNI) state with A1 symmetry is responsible for the lower resonance. Whereas, we find strong evidence for the existence of a TNI state having A1 symmetry at the 10.5 eV resonance for the first time.

A new time of flight mass spectrometer for absolute dissociative electron attachment cross-section measurements in gas phase.

A new time of flight mass spectrometer (TOFMS) has been developed to study the absolute dissociative electron attachment (DEA) cross section using a relative flow technique of a wide variety of molecules in gas phase, ranging from simple diatomic to complex biomolecules. Unlike the Wiley-McLaren type TOFMS, here the total ion collection condition has been achieved without compromising the mass resolution by introducing a field free drift region after the lensing arrangement. The field free interaction region is provided for low energy electron molecule collision studies. The spectrometer can be used to study a wide range of masses (H- ion to few hundreds atomic mass unit). The mass resolution capability of the spectrometer has been checked experimentally by measuring the mass spectra of fragment anions arising from DEA to methanol. Overall performance of the spectrometer has been tested by measuring the absolute DEA cross section of the ground state SO2 molecule, and the results are satisfactory.

Dipolar dissociation dynamics in electron collisions with carbon monoxide.

Dipolar dissociation processes in the electron collisions with carbon monoxide have been studied using time of flight (TOF) mass spectroscopy in combination with the highly differential velocity slice imaging (VSI) technique. By probing ion-pair states, both positive and/or negative ions may be detected. The ion yield curve of negative ions provides the threshold energy for the ion-pair production. On the other hand, the kinetic energy distributions and angular distributions of the fragment anion provide detailed dynamics of the dipolar dissociation process. Two ion-pair states have been identified based on angular distribution measurements using the VSI technique.

Fragmentation dynamics in dissociative electron attachment to CO probed by velocity slice imaging.

Complete dissociation dynamics in electron attachment to carbon monoxide (CO) have been studied using the newly developed velocity slice imaging (VSI) technique. Both kinetic energy and angular distributions of O(-) ions formed by dissociative electron attachment (DEA) to CO molecules have been measured for 9, 9.5, 10, 10.5, 11, and 11.5 eV incident electron energies around the resonance. Detailed observations conclusively show that two separate DEA reactions lead to the formation of O(-) ions in the ground (2)P state along with the neutral C atoms in the ground (3)P state and the first excited (1)D state, respectively. Within the axial recoil approximation and involving four partial waves, our angular distribution results clearly indicate that the two reactions leading to O(-) formation proceed through the specific resonant state(s). For the first process, more than one intermediate state is involved. On the other hand, for the second process, only one state is involved. The observed forward-backward asymmetry is explained in terms of the interference between the different partial waves that are involved in the processes.

Dissociative electron attachment to N2O using velocity slice imaging.

The structure and dynamics of the negative ion resonances leading to dissociative electron attachment in N2O are studied using the velocity slice imaging technique. Distinct momentum distributions are observed in the O(-) channel for the dominant resonances below 4 eV which are considerably different than those reported so far. Also the relatively weak but distinct resonances at 8.1 eV and 13.2 eV are studied for their dynamics for the first time. For each of these resonances two different channels of dissociation are observed with differing angular distributions.

A roaming wavepacket in the dynamics of electronically excited 2-hydroxypyridine.

How much time does it take for a wavepacket to roam on a multidimensional potential energy surface? This combined theoretical and pump-probe femtosecond time experiment on 2-hydroxypyridine proposes an answer. Bypassing the well-established transition state and conical intersection relaxation pathways, this molecular system undergoes relaxation into the S1 excited state: the central ring is destabilized by the electronic excitation, within ~100 fs after absorption of the pump photon, then the H-atom bound to oxygen undergoes a roaming behavior when it couples to other degrees of freedom of the molecule. The timescale of the latter process is measured to be ~1.3 ps. Further evolution of the wavepacket is either an oscillation onto the S1 potential or a conversion into the triplet state for timescale larger than ~110 ps. Our work introduces a new tool for the understanding of time-resolved relaxation dynamics applied to large molecules through the roaming dynamics characterized by its strongly delocalized wavepacket on flat molecular potential energy surfaces.

Atomic selectivity in dissociative electron attachment to dihalobenzenes.

We investigated electron attachment to three dihalobenzene molecules, bromochlorobenzene (BCB), bromoiodobenzene (BIB) and chloroiodobenzene (CIB), by molecular beam photoelectron spectroscopy. The most prominent product of electron attachment in the anion mass spectra was the atomic fragment of the less electronegative halogen of the two, i.e., Br(-) for BCB and I(-) for BIB and CIB. Photoelectron spectroscopy and ab initio calculations suggested that the approaching electron prefers to attack the less electronegative atom, a seemingly counterintuitive finding but consistent with the mass spectrometric result. For the iodine-containing species BIB and CIB, the photoelectron spectrum consists of bands from both the molecular anion and atomic I(-), the latter of which is produced by photodissociation of the former. Molecular orbital analysis revealed that a large degree of orbital energy reordering takes place upon electron attachment. These phenomena were shown to be readily explained by simple molecular orbital theory and the electronegativity of the halogen atoms.

Dissociative electron attachment to NO probed by velocity map imaging.

An experimental and theoretical investigation of the dissociative electron attachment process in nitric oxide is presented. Measurements using the recently developed ion momentum imaging conclusively show the presence of two resonance features in the O(-) channel. These are found to dissociate to give N atoms in the (2)D and (2)P excited states respectively, thus settling the controversies regarding the possible dissociation limits of this process. Though the angular distribution of O(-) shows the resonances contributing to these dissociations are of Π symmetry and a mixture of Π and Σ or Δ symmetry respectively, our calculations using R-matrix theory show no direct electron attachment channel leading to O(-) through these resonances, as all the allowed resonances below 10 eV decay to either O + N(-) or O(-) + N((4)S) channels. We propose that indirect mechanisms through curve crossings lead to the experimentally observed results.

Excitation mechanism in the photoisomerization of a surface-bound azobenzene derivative: Role of the metallic substrate.

Two-photon photoemission spectroscopy is employed to elucidate the electronic structure and the excitation mechanism in the photoinduced isomerization of the molecular switch tetra-tert-butyl-azobenzene (TBA) adsorbed on Au(111). Our results demonstrate that the optical excitation and the mechanism of molecular switching at a metal surface is completely different compared to the corresponding process for the free molecule. In contrast to direct (intramolecular) excitation operative in the isomerization in the liquid phase, the conformational change in the surface-bound TBA is driven by a substrate-mediated charge transfer process. We find that photoexcitation above a threshold hnu approximately 2.2 eV leads to hole formation in the Au d-band followed by a hole transfer to the highest occupied molecular orbital of TBA. This transiently formed positive ion resonance subsequently results in a conformational change. The photon energy dependent photoisomerization cross section exhibit an unusual shape for a photochemical reaction of an adsorbate on a metal surface. It shows a thresholdlike behavior below hnu approximately 2.2 eV and above hnu approximately 4.4 eV. These thresholds correspond to the minimum energy required to create single or multiple hot holes in the Au d-bands, respectively. This study provides important new insights into the use of light to control the structure and function of molecular switches in direct contact with metal electrodes.

Functional group dependent dissociative electron attachment to simple organic molecules.

Dissociative electron attachment (DEA) cross sections for simple organic molecules, namely, acetic acid, propanoic acid, methanol, ethanol, and n-propyl amine are measured in a crossed beam experiment. We find that the H(-) ion formation is the dominant channel of DEA for these molecules and takes place at relatively higher energies (>4 eV) through the core excited resonances. Comparison of the cross sections of the H(-) channel from these molecules with those from NH(3), H(2)O, and CH(4) shows the presence of functional group dependence in the DEA process. We analyze this new phenomenon in the context of the results reported on other organic molecules. This discovery of functional group dependence has important implications such as control in electron induced chemistry and understanding radiation induced damage in biological systems.

Functional group dependent site specific fragmentation of molecules by low energy electrons.

Functional group dependence is observed in the dissociative electron attachment (DEA) to various organic molecules in which the DEA features seen in the precursor molecules of the groups are retained in the bigger molecules. This functional group dependence is seen to lead to site-selective fragmentation of these molecules at the hydrogen sites. The results are explained in terms of the formation of core-excited Feshbach resonances. The results point to a simple way of controlling chemical reactions as well as interpreting the DEA data from bigger biological molecules.