Dissociation Dynamics Research Articles

Tracking ultrafast non-adiabatic dissociation dynamics of the deuterated water dication molecule.

We applied reaction microscopy to elucidate fast non-adiabatic dissociation dynamics of deuterated water molecules after direct photo-double ionization at 61eV with synchrotron radiation. For the very rare D+ + O+ + D breakup channel, the particle momenta, angular, and energy distributions of electrons and ions, measured in coincidence, reveal distinct electronic dication states and their dissociation pathways via spin-orbit coupling and charge transfer at crossings and seams on the potential energy surfaces. Notably, we could distinguish between direct and fast sequential dissociation scenarios. For the latter case, our measurements reveal the geometry and orientation of the deuterated water molecule with respect to the polarization vector that leads to this rare 3-body molecular breakup channel. Aided by multi-reference configuration-interaction calculations, the dissociation dynamics could be traced on the relevant potential energy surfaces and particularly their crossings and seams. This approach also unraveled the ultrafast time scales governing these processes.

High-Energy Reaction Dynamics of N3.

The atom-exchange and atomization dissociation dynamics for the N(4S) + N2(1Σg+) reaction are studied using a reproducing kernel Hilbert space (RKHS)-based, global potential energy surface (PES) at the MRCI-F12/aug-cc-pVTZ-F12 level of theory (MRCI, multireference configuration interaction). For the atom exchange reaction (NANB + NC → NANC + NB), computed thermal rates and their temperature dependence from quasi-classical trajectory (QCT) simulations agree to within error bars with the available experiments. Companion QCT simulations using a recently published CASPT2-based PES confirm these findings. For the atomization reaction, leading to three N(4S) atoms, the computed rates from the RKHS-PES overestimate the experimentally reported rates by 1 order of magnitude, whereas those from the permutationally invariant polynomial (PIP)-PES agree favorably, and the T dependence of both computations is consistent with the experiment. These differences can be traced back to the different methods and basis sets used. The lifetime of the metastable N3 molecule is estimated to be ∼200 fs depending on the initial state of the reactants. Finally, neural-network-based exhaustive state-to-distribution models are presented using both PESs for the atom exchange reaction. These models will be instrumental for a broader exploration of the reaction dynamics of air.

Dissociative Electron Attachment Dynamics of a Promising Cancer Drug Indicates Its Radiosensitizing Potential.

2-Bromo-1-(3,3-dinitroazetidin-1-yl)ethan-1-one (RRx-001) is a hypoxic cell chemotherapeutics with already demonstrated synergism in combined chemo-radiation therapy. The interaction of the compound with secondary low-energy electrons formed in large amounts during the physico-chemical phase of the irradiation may lead to these synergistic effects. The present study focuses on the first step of RRx-001 interaction with low-energy electrons in which a transient anion is formed and fragmented. Combination of two experiments allows us to disentangle the decay of the RRx-001 anion on different timescales. Sole presence of the electron initiates rapid dissociation of NO2 and HNO2 neutrals while NO2 - and Br- anions are produced both directly and via intermediate complexes. Based on our quantum chemical calculations, we propose that bidirectional state switching between π*(NO2) and σ*(C-Br) states explains the experimental spectra. The fast dynamics monitored will impact the condensed phase chemistry of the anion as well.

Effects of stepwise depressurisation rate on methane hydrate dissociation dynamics at pore scale using microfluidic experiments

Methane hydrate, recognized as a potential alternative energy source, faces challenges in achieving efficient production. Stepwise depressurisation has emerged as a viable technique for enhancing productivity, yet optimizing the depressurisation rate remains a complex issue. This study employs pore-scale experiments using microfluidic chips to examine the dissociation characteristics of methane hydrate under varying stepwise depressurisation rates. At a high depressurisation rate of 0.4 MPa/15 min, the dissociation process exhibits a three-stage pattern: stabilisation, rapid dissociation, and slow dissociation. During these stages, the mass transfer limitation in the water phase significantly impedes the dissociation rate. The gas-water migration triggered by depressurisation can mitigate this limitation. As the depressurisation rate is reduced to 0.2 MPa/15 min, the rapid dissociation stage splits into two due to a decrease in gas-water migration intensity. The dissociation rate decreases by 45% compared to the 0.4 MPa/15 min case. This results from an insufficient driving force for dissociation, necessitating another depressurisation step. Further reduction of the depressurisation rate to 0.1 MPa/15 min leads to a less pronounced gas-water migration, which is inadequate to significantly counteract the mass transfer limitation. As a result, the rapid dissociation phase occurring at a depressurisation rate of 0.4 MPa/15 min, which exhibits an average dissociation rate of 0.2%/s, subsequently transitions into a more uniform and slower dissociation stage, where the average rate of dissociation declines to below 0.07%/s. The experimental results offer valuable insights for guiding hydrate exploration strategies during the stepwise depressurisation process by adjusting the depressurisation rate to regulate production.

Assessing the dynamics of O2 desorption from cobalt phthalocyanine by in situ electrochemical scanning tunneling microscopy

We report here the in situ electrochemical scanning tunneling microscopy (ECSTM) study of cobalt phthalocyanine (CoPc)-catalyzed O2 evolution reaction (OER) and the dynamics of CoPc-O2 dissociation. The self-assembled CoPc monolayer is fabricated on Au(111) substrate and resolved by ECSTM in 0.1 M KOH electrolyte. The OH− adsorption on CoPc prior to OER is observed in ECSTM images. During OER, the generated O2 adsorbed on CoPc is observed in the CoPc monolayer. Potential step experiment is employed to monitor the desorption of OER-generated O2 from CoPc, which results in the decreasing surface coverage of CoPc-O2 with time. The rate constant of O2 desorption is evaluated through data fitting. The insights into the dynamics of Co-O2 dissociation at the molecular level via in situ imaging help understand the role of Co-O2 in oxygen reduction reaction (ORR) and OER.

Investigating electron-induced dissociation dynamics in the organometallic precursor Fe(CO)5: a nonadiabatic molecular dynamics approach

This research employs excited states molecular dynamics simulations to explore the electron-induced dissociation behavior of Fe(CO)5 molecules, with the specific focus on electronic excitation. The study initiates with the detailed analysis of the molecule’s stable ground state structure. Subsequent simulations reveal distinctive dissociation patterns in various bonds, particularly noting the rapid dissociation of bonds between Fe and C1, Fe and C2, while those with Fe and C3 oscillate without complete dissociation. Emphasizing the influence of the transition from the highest occupied molecular orbital to the lowest unoccupied molecular orbital on reactivity, the investigation sheds light on the charge transfer phenomenon during dissociation through Bader analysis. Insights into transitions between excited and ground states are derived from the time evolution of the Kohn–Sham orbital. This study significantly contributes to understanding intricate dissociation mechanisms under electronic excitation, especially in molecules like Fe(CO)5 characterized by complex chemical bonds. Beyond theoretical exploration, the research holds practical significance for applications in nanomaterials, such as focused electron beam-induced deposition and the fabrication of nanoscale structures, enriching our comprehension of electronic-excitation-induced dissociation and advancing both theoretical understanding and practical applications in this field.

Dynamics of the Decomposition of Gas Molecules Containing Sulfur and Nitrogen from Char-S and Char-N Structures in Combustion and Pyrolysis Reactions

ABSTRACT Combustion states of char-S (C14H16O4S) and char-N (C18H19NO3) sub function molecules in a limited number of oxygen environments and pyrolysis states at high temperatures were examined quantum mechanically. In the study, the formation of all gases, with or without carbon, were determined. All the dynamics in which the O2 molecule could be effective in the combustion mechanism and all the elements that could affect the decomposition in the pyrolysis event were determined. The dynamics of the formation and disappearance of the highly stable CO molecule and CH2O (formaldehyde) molecules were shown in detail. It has been shown that the CO molecule is a catalysis that can bond with hydrocarbon groups and decompose them into small hydrocarbon groups at high temperature. In this study, it was shown that high temperature-dependent vibration and rotational energies, CO molecule and H-atom transfers play a role in the decomposition in the pyrolysis system, and the aromatic carbon ring group is the last particle group to decompose. In addition, the formation and dissociation dynamics of sulfoxylic acid, thioformic acid, hydrogen sulfide molecules originating from the Char-S system, as well as the formation conditions of hydrogen cyanide and pyridinyl molecules originating from the Char-N system, were determined. The study also showed that since the N-atom is located in the aromatic carbon ring, it makes the emergence of the nitrous oxide molecule difficult in pyrolysis systems.

Correlated electron-nuclear dynamics of photoinduced water dissociation on rutile TiO2.

Elucidating the mechanism of photoinduced water splitting on TiO2 is important for advancing the understanding of photocatalysis and the ability to control photocatalytic surface reactions. However, incomplete experimental information and complex coupled electron-nuclear motion make the microscopic understanding challenging. Here we analyse the atomic-scale pathways of photogenerated charge carrier transport and photoinduced water dissociation at the prototypical water-rutile TiO2(110) interface using first-principles dynamics simulations. Two distinct mechanisms are observed. Field-initiated electron migration leads to adsorbed water dissociation via proton transfer to a surface bridging oxygen. In the other pathway, adsorbed water dissociation occurs via proton donation to a second-layer water molecule coupled to photoexcited-hole transfer promoted by in-plane surface lattice distortions. Two stages of non-adiabatic in-plane lattice motion-expansion and recovery-are observed, which are closely associated with population changes in Ti3d orbitals. Controlling such highly correlated electron-nuclear dynamics may provide opportunities for boosting the performance of photocatalytic materials.

Anisotropic Photodetachment of Positronium Negative Ions with Linearly Polarized Light.

We report on the anisotropic photodetachment of positronium negative ions, followed by the dissociation into p-wave electrons and positronium atoms, with a linearly polarized laser beam. We have observed a strong recoil effect of the photoelectrons on the translation momentum of the dissociated positronium atoms. With polarization angle-resolved measurements, the asymmetry parameter of the photoemission angular distribution of the ions at a photon energy of 1.165eV was determined to be 1.97±0.04(stat)±0.07(syst), in agreement with a theoretical prediction. The present method can be applied to explore the unrevealed dissociation dynamics of exotic particle systems and their manipulation with polarized light.

Effect of pH and Shear on Heat-Induced Changes in Milk Protein Concentrate Suspensions.

The effect of shear on heat-induced changes in milk protein concentrate suspensions was examined at different pH levels, revealing novel insights into micellar dissociation and protein aggregation dynamics. Milk protein concentrate suspensions, adjusted to pH of 6.1, 6.4, 6.8, or 7.5, underwent combined heat (90 °C for 5 min or 121 °C for 2.6 min) and shear (0, 100, or 1000 s-1) treatment. The fragmentation of protein aggregates induced by shear was evident in the control MPC suspensions at pH 6.8, irrespective of the temperature. At pH 7.5, shear increased the heat-induced micellar dissociation. This effect was particularly pronounced at 121 °C and 1000 s-1, resulting in reduced particle size and an elevated concentration of κ-casein (κ-CN) in the non-sedimentable phase. At pH 6.1 or 6.4, shear effects were dependent on sample pH, thereby modifying electrostatic interactions and the extent of whey protein association with the micelles. At pH 6.1, shear promoted heat-induced aggregation, evidenced by an increase in particle size and a significant decline in both whey proteins and caseins in the non-sedimentable phase. At pH 6.4, shear-induced fragmentation of aggregates was observed, prominently due to comparatively higher electrostatic repulsions and fewer protein interactions. The influence of shear on heat-induced changes was considerably impacted by initial pH.

Investigation of the MDM2-binding potential of de novo designed peptides using enhanced sampling simulations

The tumor suppressor p53 plays a crucial role in cellular responses to various stresses, regulating key processes such as apoptosis, senescence, and DNA repair. Dysfunctional p53, prevalent in approximately 50 % of human cancers, contributes to tumor development and resistance to treatment. This study employed deep learning-based protein design and structure prediction methods to identify novel high-affinity peptide binders (Pep1 and Pep2) targeting MDM2, with the aim of disrupting its interaction with p53. Extensive all-atom molecular dynamics simulations highlighted the stability of the designed peptide in complex with the target, supported by several structural analyses, including RMSD, RMSF, Rg, SASA, PCA, and free energy landscapes. Using the steered molecular dynamics and umbrella sampling simulations, we elucidate the dissociation dynamics of p53, Pep1, and Pep2 from MDM2. Notable differences in interaction profiles were observed, emphasizing the distinct dissociation patterns of each peptide. In conclusion, the results of our umbrella sampling simulations suggest Pep1 as a higher-affinity MDM2 binder compared to p53 and Pep2, positioning it as a potential inhibitor of the MDM2-p53 interaction. Using state-of-the-art protein design tools and advanced MD simulations, this study provides a comprehensive framework for rational in silico design of peptide binders with therapeutic implications in disrupting MDM2-p53 interactions for anticancer interventions.

Bond analysis in meta- and para-substituted thiophenols: overlap descriptors, local mode analysis, and QTAIM.

This study delves into the chemical nuances of thiophenols and their derivatives through a comprehensive computational analysis, moving beyond traditional energetic perspectives such as bond dissociation enthalpy and S-H dissociation dynamics. By employing the overlap model along with its topological descriptors (OP/TOP), quantum theory of atoms in molecules (QTAIM), and local vibrational mode (LVM) theories, the research provides a deeper understanding of the S-H and C-S bonding scenarios in substituted thiophenols. The investigation follows the electron-donating capacity of S-H substituent variation with the nature and positioning of other ring substituents. Energy profile analyses indicate distinct stability differences in the cis and trans conformations of meta- and para-PhSH systems, influenced by the electron-donating strength of these substituents. The study also uncovers significant variations in S-H bond distances and descriptor values, particularly in para-substituted PhSH, reflecting the influence of electron-donating or withdrawing substituents. In contrast, alterations at the meta-position show minimal effects on C-S bond descriptors, while para-substitutions markedly influence C-S bond characteristics, demonstrating a clear correlation with the electron-donating or withdrawing capabilities of the substituents. This research sheds light on the intricate bond dynamics in aromatic systems with diverse substituents, highlighting the complex interaction between electronic effects and molecular conformation. The study employs the B97X-D/Def2TZVP level of theory for molecular geometries, ensuring accurate characterization of structures as true minima via analytical harmonic frequency determination. The electronic properties of S-H and C-S bonds in variously substituted thiophenols were analyzed using OP/TOP, QTAIM, and LVM methodologies. Computational processes, including conformational scans, geometry optimizations, and vibrational frequency calculations, were conducted using Gaussian 09, with ultra-fine integration grids and tight convergence criteria for the SCF procedure. Bond descriptors were computed utilizing ChemBOS, Multiwfn, and LModeA software, providing a robust and detailed examination of bond properties.

Isomer-resolved unimolecular dynamics of the hydroperoxyalkyl intermediate (•QOOH) in cyclohexane oxidation

The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C6H11O2), building on higher-level reference calculations for the smaller ethane oxidation (C2H5O2) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.

Theoretical Investigation on Electronic Excited States of the HSO Radical.

HSO radicals play an important role in the photochemical processes in combustion, the atmosphere, and the interstellar medium. In this work, we perform a high-level ab initio study on the electronic excited states of HSO using the internally contracted multireference configuration interaction methods including Davidson correction (icMRCI + Q) in combination with the correlation-consistent basis sets. The molecular geometries, vertical transition energies, oscillator strengths, and electronic configurations of 19 electronic states of HSO are computed. The electronic potential energy curves of HSO along the bond lengths and bond angles are presented. Based on our calculations, the interactions between the electronic states involved in the ultraviolet region and the mechanism of photodissociation are discussed, which will lay a foundation for revealing the dissociation dynamics of gas-phase HSO molecules in outer space and the earth's atmosphere.

Gallium Trichloride Fluid: Dimer Dissociation Mechanism, Local Structure, and Atomic Dynamics.

Molten gallium trichloride emerges as a promising solvent for oxidative metal recycling. The use of supercritical fluid enhances the performance and kinetics of metal dissolution due to significantly lower viscosity in the reaction media. Additionally, the dual molecular nature of gallium trichloride, existing as edge-sharing ES-Ga2Cl6 dimers at low temperatures and high pressure, or flat trigonal GaCl3 monomers in the vicinity of the critical point and low pressures, creates the possibility to tailor the chemical geometry to a particular metallic species. Nevertheless, the mechanism of dimer dissociation, local structure, and atomic dynamics in supercritical gallium trichloride fluids are not known. Using first-principles molecular dynamics, validated by comparison with our high-energy X-ray diffraction results, we illustrate the elementary steps in dimer dissociation. These include the formation of intermediate corner-sharing CS-Ga2Cl6 dimers, the partial disproportionation of GaCl3 monomers at high temperatures and low pressures, changes in the local environment of molecular entities, and unusual atomic dynamics in supercritical fluids.

C-terminal Domain of T4 gene 32 Protein Enables Rapid Filament Reorganization and Dissociation

Bacteriophage T4 gene 32 protein (gp32) is a single-stranded DNA (ssDNA) binding protein essential for DNA replication. gp32 forms stable protein filaments on ssDNA through cooperative interactions between its core and N-terminal domain. gp32′s C-terminal domain (CTD) is believed to primarily help coordinate DNA replication via direct interactions with constituents of the replisome. However, the exact mechanisms of these interactions are not known, and it is unclear how tightly-bound gp32 filaments are readily displaced from ssDNA as required for genomic processing. Here, we utilized truncated gp32 variants to demonstrate a key role of the CTD in regulating gp32 dissociation. Using optical tweezers, we probed the binding and dissociation dynamics of CTD-truncated gp32, *I, to an 8.1 knt ssDNA molecule and compared these measurements with those for full-length gp32. The *I-ssDNA helical filament becomes progressively unwound with increased protein concentration but remains significantly more stable than that of full-length, wild-type gp32. Protein oversaturation, concomitant with filament unwinding, facilitates rapid dissociation of full-length gp32 from across the entire ssDNA segment. In contrast, *I primarily unbinds slowly from only the ends of the cooperative clusters, regardless of the protein density and degree of DNA unwinding. Our results suggest that the CTD may constrain the relative twist angle of proteins within the ssDNA filament such that upon critical unwinding the cooperative interprotein interactions largely vanish, facilitating prompt removal of gp32. We propose a model of CTD-mediated gp32 displacement via internal restructuring of its filament, providing a mechanism for rapid ssDNA clearing during genomic processing.

Boosting exciton dissociation and charge transfer in CsPbBr3 QDs via ferrocene derivative ligation for CO2 photoreduction

Photo-catalytic CO2 reduction with perovskite quantum dots (QDs) shows potential for solar energy storage, but it encounters challenges due to the intricate multi-electron photoreduction processes and thermodynamic and kinetic obstacles associated with them. This study aimed to improve photo-catalytic performance by addressing surface barriers and utilizing multiple-exciton generation in perovskite QDs. A facile surface engineering method was employed, involving the grafting of ferrocene carboxylic acid (FCA) onto CsPbBr3 (CPB) QDs, to overcome limitations arising from restricted multiple-exciton dissociation and inefficient charge transfer dynamics. Kelvin Probe Force Microscopy and XPS spectral confirmed successfully creating an FCA-modulated microelectric field through the Cs active site, thus facilitating electron transfer, disrupting surface barrier energy, and promoting multi-exciton dissociations. Transient absorption spectroscopy showed enhanced charge transfer and reduced energy barriers, resulting in an impressive CO2-to-CO conversion rate of 132.8 μmol g-1 h-1 with 96.5% selectivity. The CPB-FCA catalyst exhibited four-cycle reusability and 72 h of long-term stability, marking a significant nine-fold improvement compared to pristine CPB (14.4 μmol g-1 h-1). These results provide insights into the influential role of FCA in regulating intramolecular charge transfer, enhancing multi-exciton dissociation, and improving CO2 photoreduction on CPB QDs. Furthermore, these findings offer valuable knowledge for controlling quantum-confined exciton dissociation to enhance CO2 photocatalysis.

Unveiling the exciton dissociation dynamics steered by built-in electric fields in conjugated microporous polymers for photoreduction of uranium (VI) from seawater

Developing highly efficient photocatalysts based on conjugated microporous polymers (CMPs) are often impeded by the intrinsically large exciton binding energy and sluggish charge transfer kinetics that result from their vulnerable driving force. Herein, a family of pyrene-based nitrogen-implanted CMPs were constructed, where the nitrogen gradient was regulated. Accordingly, the built-in electric field endowed by the nitrogen gradient dramatically accelerates the dissociation of exciton into free carriers, thereby enhancing charge separation efficiency. As a result, PyCMP-3N generated by polymerization of 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine featured an optimized built-in electric field and exhibited the highest photocatalytic removal efficiency of uranium (VI) (99.5 %). Our proposed strategy not only provides inspiration for constructing the built-in electric field by controlling nitrogen concentration gradients, but also offers an in-depth understanding the crucial role of built-in electric field in exciton dissociation and charge transfer, efficiently promoting CMPs photocatalysis.

Oncogenic changes in histones and their impact on nucleosome dissociation and H2B tail structure and dynamics

Oncogenic changes in histones and their impact on nucleosome dissociation and H2B tail structure and dynamics

Contrasting Dynamics in Isoelectronic Anions Formed by Electron Attachment.

Cyanogen NCCN and cyanoacetylene HCCCN are isoelectronic molecules, and as such, they have many similar properties. We focus on the bond cleavage in these induced by the dissociative electron attachment. In both molecules, resonant electron attachment produces CN- with very similar energy dependence. We investigate the very different dissociation dynamics, in each of the two molecules, revealed by velocity map imaging of this common fragment. Different dynamics are manifested both in the excess energy partitioning and in the angular distributions of fragments. Based on the comparison with electron energy loss spectra, which provide information about possible parent states of the resonances (both optically allowed and forbidden excited states of the neutral target), we ascribe the observed effect to the distortion of the nuclear frame during the formation of core-excited resonance in cyanoacetylene. The proposed mechanism also explains a puzzling difference in the magnitude of the CN- cross section in the two molecules which has been so far unexplained.