Roaming Dynamics Research Articles

Helium roaming in excess electrons in C60F60 as dynamic quasi-Matryoshka dolls.

Multi-guest clathrates exhibit lots of functional characteristics owing to their unique structures, which herald beautiful application prospects, but their fundamental information is still scarce. Herein, we explore a type of (helium, excess electrons/EEs)-C60F60 co-clathrates with quasi-Matryoshka-doll structures using abinitio molecular dynamics simulation and reveal the EEs-entangled He roaming dynamics in C60F60 and its effect on the characteristics of clathrates. Perfluorination ensures that C60F60 possesses an extremely electropositive interior cavity. Its unique confinement effect can stabilize He as an extremely inert entity by noticeably enlarging the 1s-2s orbital gap and can also trap 1-2 EEs in its s-type interior orbital with extremely large binding energies. Co-inclusion of He and EEs in C60F60 exhibits inter-repulsive He⋯EEs entangling dynamics featuring quasi-Matryoshka-doll structures (He@EEs@C60F60). In this structure, EEs screen the attraction of cage-shell Cδ+ to He 1s2 electrons, thus inhibiting their stabilization and orbital expansion, while He conversely decreases the stability of EEs and redshifts their transition absorption. He can roam in the cavity, but its trajectory is impacted by EEs serving as a medium, and thus, the structures exhibit anormal dynamic variation of internuclear He⋯C spin coupling JHeC, which is manipulated by the EEs-entangled He roaming dynamics. JHeC and JHeC' present opposite distance dependences for the colinearly aligned C⋅⋅⋅He⋅⋅⊗⋅⋅⋅⋅⋅C' (⊗, the cage center). This work provides insights into the Matryoshka-doll structured He@EEs@C60F60 with He-EEs entangling dynamics and its modulation on EEs absorption and reveals the dynamic role of EEs in manipulating He-roaming and JHeC coupling properties for promising applications.

Molecular Association and Reactivity of the Pyridine Dimer Cation.

A recent experimental report has identified the formation of the C-N hemibonded pyridine dimer cation following vacuum ultraviolet near-threshold photoionization [J. Phys. Chem. Lett., 2021, 12, 4936-4943]. Herein, the dynamics and consequent reactivity of the pyridine dimer cation were investigated employing Born-Oppenheimer molecular dynamics (BOMD) simulations. An antiparallel π-stacked pyridine dimer in the neutral ground state is transformed into a noncovalently interacting C-H···N hydrogen-bonded structure which can lead to proton transfer in the cationic state. Additionally, C-N- and N-N-bonded adducts were formed in the cationic state. Further, metastable C-H···H-C-bonded cationic species was observed, which rearranged to an N-N bonded adduct. In contrast to the experimental observation, migration of the proton to the α position was not observed in the C-N bonded adduct owing to a high barrier of about 2 eV. The observed trends in the molecular association, proton transfer, and the formation of C-N and N-N bonded adducts are a consequence of the roaming dynamics of one pyridine moiety over the other in the cationic state.

Roaming in acetaldehyde.

We investigate roaming in the photodissociation of acetaldehyde (CH3CHO), providing insights into the contrasting roaming dynamics observed for this molecule compared to formaldehyde. We carry out trajectory studies for full-dimensional acetaldehyde, supplemented with an analysis of a two-degree-of-freedom restricted model and obtain evidence for two distinct roaming pathways. Trajectories exhibit roaming at both shorter (9-11.5 au) and larger (14.5-22.9 au) maximum CH3-HCO separations, characterized by differing amounts of HCO rotation. No roaming trajectories were found in the intervening gap region. The roaming dynamics near 14.5-22.9 au are well-reproduced by the restricted model and involve passage through a centrifugal barrier, analogous to formaldehyde roaming. However, the shorter-range 9-11.5 au roaming appears unique to acetaldehyde and is likely facilitated by repulsive interactions absent in the simplified models. Phase space analysis reveals that this additional roaming pathway is inaccessible in the reduced dimensionality system. The findings suggest that acetaldehyde's increased propensity for roaming compared to formaldehyde may arise from the presence of multiple distinct roaming mechanisms rather than solely the higher roaming fragment mass.

Roaming in highly excited states: The central atom elimination of triatomic molecule decomposition.

Chemical reactions are generally assumed to proceed from reactants to products along the minimum energy path (MEP). However, straying from the MEP-roaming-has been recognized as an unconventional reaction mechanism and found to occur in both the ground and first excited states. Its existence in highly excited states is however not yet established. We report a dissociation channel to produce electronically excited fragments, S(1D)+O2(a1Δg), from SO2 photodissociation in highly excited states. The results revealed two dissociation pathways: One proceeds through the MEP to produce vibrationally colder O2(a1Δg) and the other yields vibrationally hotter O2(a1Δg) by means of a roaming pathway involving an intramolecular O abstraction during reorientation motion. Such roaming dynamics may well be the rule rather than the exception for molecular photodissociation through highly excited states.

Roaming Dynamics in Hydroxymethyl Hydroperoxide Decomposition Revealed by the Full-Dimensional Potential Energy Surface of the CH2OO + H2O Reaction.

The CH2OO + H2O reaction is an important atmospheric process that leads to the formation of formic acid (HCOOH) and water via the intermediate hydroxymethyl hydroperoxide (HOCH2OOH, HMHP). We investigated the intricacies of this process by employing quasiclassical trajectory calculations on an accurate, full-dimensional ab initio potential energy surface (PES). In addition to the direct mechanism via the transition state (TS), an interesting roaming mechanism was found to play the predominant role in producing H2O and HCOOH. This roaming pathway is featured as the near direct dissociation of HMHP into OH and hydroxymethoxy radical, followed by the retraction of OH and abstraction of the H atom, culminating in the formation of H2O. Due to the longer interaction time of the roaming mechanism, less product translational energy was released, but more internal energies of HCOOH were obtained, as compared with the direct TS mechanism. The enhanced yield of H2O and formic acid achieved through roaming dynamics underscores the significance of dynamics simulations based on an accurate full-dimensional PES. This work provides new insights into the dynamics of the CH2OO + H2O reaction and its implications for atmospheric chemistry.

Dynamics of Hydrogen Bond Breaking Induced by Outer-Valence Intermolecular Coulombic Decay

The photoexcitation of weakly bound complexes can lead to several decay pathways, depending on the nature of the potential energy surfaces. Upon excitation of a chromophore in a weakly bound complex, ionization of its neighbor upon energy transfer can occur due to a unique relaxation process known as intermolecular Coulombic decay (ICD), a phenomenon of renewed focus owing to its relevance in biological systems. Herein, we report the evidence for outer-valence ICD induced by multiphoton excitation by near-ultraviolet radiation of 4.4 eV photons, hitherto unknown in molecular systems. In the binary complexes of 2,6-difluorophenylacetylene with aliphatic amines, a resonant two-photon excitation localized on the 2,6-difluorophenylacetylene chromophore results in the formation of an amine cation following an outer-valence ICD process. The unique trends in experimentally observed translational energy distribution profiles of the amine cations following hydrogen bond dissociation, analyzed with the help of electronic structure and ab initio molecular dynamics calculations, revealed the presence of a delicate interplay of roaming dynamics, methyl-rotor dynamics, and binding energy.

Roaming dynamics of H+C2D2 reaction on fundamental-invariant neural network potential energy surface

We performed extensive quasiclassical trajectory calculations for the H+C2D2→HD+C2D/D2+C2H reaction based on a recently developed, global and accurate potential energy surface by the fundamental-invariant neural network method. The direct abstraction pathway plays a minor role in the overall reactivity, which can be negligible as compared with the roaming pathways. The acetylene-facilitated roaming pathway dominates the reactivity, with very small contributions from the vinylidene-facilitated roaming. Although the roaming pathways proceed via the short-lived or long-lived complex forming process, the computed branching ratio of product HD to D2 is not far away from 2:1, implying roaming dynamics for this reaction is mainly contributed from the long-lived complex-forming process. The resulting angular distributions for the two product channels are also quite different. These computational results give valuable insights into the significance and isotope effects of roaming dynamics in the biomolecular reactions.

Quantum resonances and roaming dynamics in formaldehyde photodissociation.

The unimolecular dissociation of formaldehyde is studied via excitation to the à band at several excitation energies from just below the ground state radical dissociation threshold to 5000 cm-1 above it. CO product rotational distributions, photofragment excitation spectroscopy and state-correlated slice imaging results are combined with quasi-classical trajectory calculations to reveal manifestations of quantum effects in this complex dissociation process involving interactions among radical, molecular, and roaming pathways. Evidence of nodal structure at the tight transition state to molecular products is investigated and correlations between the CO rotational and H2 vibrational distributions are used to suggest the transition state modes that are responsible. A large modulation of the roaming yield previously identified and associated with roaming resonances at the onset of the H + HCO(v1,v2,v3 = 0,0,0) product channel suggests a similar origin for enhanced roaming and a roaming yield that is strongly dependent on parent rotation on the 2641 band just 15 cm-1 above the H + HCO(0,2,1) threshold. Similar resonances are predicted on other bands that share near coincident energies with HCO product vibrational thresholds.

Cover: Journal of the Chinese Chemical Society 8/2021

In this figure, H2CO as an example shows both transition state and roaming pathways in the photodissociation (H2COàH2 + CO). The developed multi‐center impulsive model was successfully applied to predict the translational energy distribution and fragment angular correlation characterizing both transition state and roaming dynamics, in comparison with the quasi‐classical trajectory calculations. Prof. King‐Chuen Lin and his co‐workers on page 1358–1378 in this issue.image

Vibrational energy levels of the S 0 and S 1 states of formaldehyde using an accurate ab initio based global diabatic potential energy matrix

Low-lying vibrational energy levels of both the ground (S 0) and first excited singlet (S 1) states of formaldehyde have been determined using an exact kinetic energy operator and adiabatic potential energy surfaces derived from a recently developed full-dimensional global diabatic potential energy matrix (DPEM) based on a neural network representation of high level ab initio data. The agreement with available experimental band origins provides strong evidence in support of the accuracy of the DPEM, which can be used in the future for understanding the internal conversion of H2CO(S 1) and the subsequent roaming dynamics on its S 0 state.

Capturing roaming molecular fragments in real time.

Since the discovery of roaming as an alternative molecular dissociation pathway in formaldehyde (H2CO), it has been indirectly observed in numerous molecules. The phenomenon describes a frustrated dissociation with fragments roaming at relatively large interatomic distances rather than following conventional transition-state dissociation; incipient radicals from the parent molecule self-react to form molecular products. Roaming has been identified spectroscopically through static product channel-resolved measurements, but not in real-time observations of the roaming fragment itself. Using time-resolved Coulomb explosion imaging (CEI), we directly imaged individual "roamers" on ultrafast time scales in the prototypical formaldehyde dissociation reaction. Using high-level first-principles simulations of all critical experimental steps, distinctive roaming signatures were identified. These were rendered observable by extracting rare stochastic events out of an overwhelming background using the highly sensitive CEI method.

Revealing roaming on the double Morse potential energy surface with Lagrangian descriptors

In this paper, we analyse the phase space structure of the roaming dynamics in a 2 degree of freedom potential energy surface consisting of two identical planar Morse potentials separated by a distance. This potential energy surface was previously studied in Carpenter B K et al (2018 Regul. Chaotic Dyn. 23 60–79), and it has two potential wells surrounded by an unbounded flat region containing no critical points. We study the phase space mechanism for the transference between the wells using the method of Lagrangian descriptors.

Roaming Reactions and Dynamics in the van der Waals Region.

Roaming reactions were first clearly identified in photodissociation of formaldehyde 15 years ago, and roaming dynamics are now recognized as a universal aspect of chemical reactivity. These reactions typically involve frustrated near-dissociation of a quasibound system to radical fragments, followed by reorientation at long range and intramolecular abstraction. The consequences can be unexpected formation of molecular products, depletion of the radical pool in chemical systems, and formation of products with unusual internal state distributions. In this review, I examine some current aspects of roaming reactions with an emphasis on experimental results, focusing on possible quantum effects in roaming and roaming dynamics in bimolecular systems. These considerations lead to a more inclusive definition of roaming reactions as those for which key dynamics take place at long range.

Simplified Representation of Multichannel Thermal Unimolecular Reactions. II. Refined Parametrization of Formaldehyde Dissociation

Abstract Simplified representations of branching fractions for thermal unimolecular two-channel reactions are discussed. The dissociation of formaldehyde serves as an illustrative example. Quantum-corrected classical trajectory calculations on an ab initio potential energy surface are combined with master equation calculations for collisional energy transfer. The treatment accounts for roaming atom dynamics. The dependence of the channel branching fractions on the bath gas pressure and temperature, on the collision efficiencies, and on the difference of channel threshold energies, are explored. It is discussed to what extent the derived simplified representations of channel branching fractions can be generalized.

Collision-induced and complex-mediated roaming dynamics in the H + C2H4 → H2 + C2H3 reaction.

Roaming is a novel mechanism in reaction dynamics. It describes an unusual pathway, which can be quite different from the conventional minimum-energy path, leading to products. While roaming has been reported or suggested in a number of unimolecular reactions, it has been rarely reported for bimolecular reactions. Here, we report a high-level computational study of roaming dynamics in the important bimolecular combustion reaction H + C2H4 → H2 + C2H3, using a new, high-level machine learning-based potential energy surface. In addition to the complex-mediated roaming mechanism, a non-complex forming roaming mechanism is found. It can be described as a direct inelastic collision where the departing H atom roams and then abstracts an H atom. We denoted this as “collision-induced” roaming. These two roaming mechanisms have different angular distributions; however, both produce highly internally excited C2H3. The roaming pathway leads to remarkably different dynamics as compared with the direct abstraction pathway. A clear signature of the roaming mechanism is highly internally excited C2H3, which could be observed experimentally.

Universal crossed beam imaging studies of polyatomic reaction dynamics.

The marriage between high level quantum calculations and experimental advances in laser technology, quantum state control, and detection techniques have opened the door to the study of molecular collision dynamics at a new level of detail. However, one current challenge lies in adapting these powerful strategies to address questions beyond the scope of the small ground state systems that have largely been the focus of reaction dynamics investigations to-date. For molecules with intermediate or large size (more than 6 atoms), lack of spectroscopic information and spectral congestion limit quantum state preparation, control and detection for experiment, and the large number of degrees of freedom of the system makes accurate quantum dynamics calculations prohibitively expensive. Nevertheless, studies of the chemical dynamics of such systems can reveal novel aspects of reactivity not anticipated based upon the behavior of smaller model systems. This Perspective will highlight applications of soft vacuum ultraviolet photoionization at 157 nm as a universal probe in combination with crossed beams and DC slice velocity map ion imaging to study bimolecular reaction dynamics of molecules of intermediate or large size, illuminated with support of high-level ab initio calculations. Here, we report on the chemical dynamics of atomic oxygen or chlorine reactions with organic compounds: propanol isomers, alkylamines (N(CH3)3 and NH(CH3)2), and isobutene ((CH3)2CCH2) studied using this approach. The polyatomic radical products from the hydrogen abstraction process have been detected by 157 nm photoionization and their slice ion images embody translational energy and angular information that directly reflect the underlying collision dynamics. Various reaction mechanisms (such as direct abstraction and addition-elimination) along with the involvement of roaming dynamics and novel intersystem crossing pathways are presented. These demonstrate the power of this technique to reveal fundamentally new aspects of reaction dynamics that arise in larger reaction systems.

Roaming at Constant Kinetic Energy: Chesnavich’s Model and the Hamiltonian Isokinetic Thermostat

We consider the roaming mechanism for chemical reactions under the nonholonomic constraint of constant kinetic energy. Our study is carried out in the context of the Hamiltonian isokinetic thermostat applied to Chesnavich's model for an ion-molecule reaction. Through an analysis of phase space structures we show that imposing the nonholonomic constraint does not prevent the system from exhibiting roaming dynamics, and that the origin of the roaming mechanism turns out to be analogous to that found in the previously studied Hamiltonian case.

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

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

The phase space geometry underlying roaming reaction dynamics

Recent studies have found an unusual way of dissociation in formaldehyde. It can be characterized by a hydrogen atom that separates from the molecule, but instead of dissociating immediately it roams around the molecule for a considerable amount of time and extracts another hydrogen atom from the molecule prior to dissociation. This phenomenon has been coined roaming and has since been reported in the dissociation of a number of other molecules. In this paper we investigate roaming in Chesnavich’s hbox {CH}_4^+ model. During dissociation the free hydrogen must pass through three phase space bottleneck for the classical motion, that can be shown to exist due to unstable periodic orbits. None of these orbits is associated with saddle points of the potential energy surface and hence related to transition states in the usual sense. We explain how the intricate phase space geometry influences the shape and intersections of invariant manifolds that form separatrices, and establish the impact of these phase space structures on residence times and rotation numbers. Ultimately we use this knowledge to attribute the roaming phenomenon to particular heteroclinic intersections.

Formaldehyde roaming dynamics: Comparison of quasi-classical trajectory calculations and experiments.

The photodissociation dynamics of roaming in formaldehyde are studied by comparing quasi-classical trajectory calculations performed on a new potential energy surface (PES) to new and detailed experimental results detailing the CO + H2 product state distributions and their correlations. The new PES proves to be a significant improvement over the past one, now more than a decade old. The new experiments probe both the CO and H2 products of the formaldehyde dissociation. The experimental and trajectory data offer unprecedented detail about the correlations between internal states of the CO and H2 dissociation products as well as information on how these distributions are different for the roaming and transition-state pathways. The data investigated include, for dissociation on the formaldehyde 2143 band, (a) the speed distributions for individual vibrational/rotational states of the CO products, providing information about the correlated internal energy distributions of the H2 product, and (b) the rotational and vibrational distributions for the CO and H2 products as well as the contributions to each from both the transition state and roaming channels. The agreement between the trajectory and experimental data is quite satisfactory, although minor differences are noted. The general agreement provides support for future use of the experimental techniques and the new PES in understanding the dynamics of photodissociative processes.