Bond-selective effect for the dissociative chemisorption of HOD on the Ni(100) surface revealed at the full-dimensional quantum dynamical level.

We present a comprehensive investigation into the dissociative chemisorption of HOD on a rigid Ni(100) surface using an approximate full-dimensional (9D) quantum dynamics approach, which was based on the time-dependent wave-packet calculations on a full-dimensional potential energy surface obtained through neural network fitting to density functional theory energy points. The approximate-9D probabilities were computed by averaging the seven-dimensional (7D) site-specific dissociation probabilities across six impact sites with appropriate relative weights. Our results uncover a distinctive bond-selective effect, demonstrating that the vibrational excitation of a specific bond substantially enhances the cleavage of that excited bond. The product branching ratios are substantially influenced by which bond undergoes excitation, exhibiting a clear preference for the product formed through the cleavage of the excited bond over the alternative product.

Supercollisions of NaCl + NaCl on an Accurate Full-Dimensional Potential Energy Surface.

An accurate, global, full-dimensional potential energy surface (PES) of NaCl + NaCl has been constructed by the fundamental invariant-neural network (FI-NN) fitting based on roughly 13,000 ab initio energies at the level of CCSD(T)-F12a/aug-cc-pVTZ, with the small fitting error of 0.16 meV. Extensive quasiclassical trajectory (QCT) calculations were performed on this PES to investigate the energy transfer process of the NaCl + NaCl collision at four different collision energies. Various quantities were obtained, including the cross-sections, energy transfer probability, average energy transfer, and collision lifetime. The probabilities of energy transfer (P(ΔE)) for prompt trajectories, nonreactive trajectories, and reactive trajectories deviate from a simple exponential decay pattern. Instead, a noteworthy probability is observed in the high-energy transfer region, indicative of supercollisions. The formation of the (NaCl)2 complex, coupled with a comparatively extended collision lifetime, promotes vibrational excitation in NaCl molecules. The reactive trajectories exhibit enhanced energy transfer, attributed to the longer lifetime of the NaCl dimer. This study not only provides an accurate and extensive understanding of the NaCl + NaCl collision dynamics but also reveals intriguing phenomena, such as supercollisions and enhanced energy transfer in reactive trajectories, shedding light on the complex intricacies of molecular interactions.

Observation of geometric phase effect through backward angular oscillations in the H + HD → H2 + D reaction.

Quantum interference between reaction pathways around a conical intersection (CI) is an ultrasensitive probe of detailed chemical reaction dynamics. Yet, for the hydrogen exchange reaction, the difference between contributions of the two reaction pathways increases substantially as the energy decreases, making the experimental observation of interference features at low energy exceedingly challenging. We report in this paper a combined experimental and theoretical study on the H + HD → H2 + D reaction at the collision energy of 1.72 eV. Although the roaming insertion pathway constitutes only a small fraction (0.088%) of the overall contribution, angular oscillatory patterns arising from the interference of reaction pathways were clearly observed in the backward scattering direction, providing direct evidence of the geometric phase effect at an energy of 0.81 eV below the CI. Furthermore, theoretical analysis reveals that the backward interference patterns are mainly contributed by two distinct groups of partial waves (J ~ 10 and J ~ 19). The well-separated partial waves and the geometric phase collectively influence the quantum reaction dynamics.

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.

Six-dimensional quantum dynamics study for the dissociative chemisorption of H2 on pure and alloyed AgAu surfaces.

The 6D time-dependent wave packet calculations were performed to explore H2 dissociation on Ag, Au, and two AgAu alloy surfaces, using four newly fitted potential energy surfaces based on the neural network fitting to density functional theory energy points. The ligand effect resulting from the Ag-Au interaction causes a reduction in the barrier height for H2+Ag/Au(111) compared to H2+Ag(111). However, the scenario is reversed for H2+Au/Ag(111) and H2+Au(111). The 6D dissociation probabilities of H2 on Ag/Au(111) surfaces are significantly higher than those on the pure Ag(111) surface, but the corresponding results for H2 on Au/Ag(111) surfaces are substantially lower than those on the pure Au(111) surface. The reactivity of H2 on Au(111) is larger than that on Ag(111), despite Ag(111) having a slightly lower static barrier height. This can be attributed to the exceptionally small dissociation probabilities at the hcp and fcc regions, which are at least 100 times smaller compared to those at the bridge or top site for H2+Ag(111). Due to the late barrier being more pronounced, the vibrational excitation of H2 on Ag(111) is more effective in promoting the reaction than on Au(111). Moreover, a high degree of alignment dependence is detected for the four reactions, where the H2 dissociation has the highest probability at the helicopter alignment, as opposed to the cartwheel alignment.

Charge-Transfer-Controlled Quantum Dynamics of HCl Dissociation on the Ag/Au(111) Bimetallic Alloy Surface.

Understanding polar molecule dynamics on bimetallic surfaces, especially electropositivity and electronegativity, remains a challenge. Here, we report the reactivity of HCl on a strained Ag monolayer on Au(111) using six-dimensional quantum dynamics with a new machine-learning-based potential energy surface. Surprisingly, HCl reactivity is significantly suppressed by the Ag-Au interaction despite a lower HCl+Ag/Au(111) barrier than pure Ag(111). This arises from charge transfer between Ag and Au, where electronegative Au makes the top Ag layer on Ag/Au(111) electropositive, unlike that on pure Ag(111). Electropositive Ag in HCl+Ag/Au(111) attracts Cl, yielding an unfavorable H-Cl configuration and reduced reactivity. These findings deepen our understanding of polar molecule interactions on bimetallic surfaces, highlighting the role of charge transfer in dissociative chemisorption and the implications for catalyst design in heterogeneous catalysis.

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.

Multiple Dissociation Pathways in HNCO Decomposition Governed by Potential Energy Surface Topography.

The exquisite features of molecular photochemistry are key to any complete understanding of the chemical processes governed by potential energy surfaces (PESs). It is well established that multiple dissociation pathways relate to nonadiabatic transitions between multiple coupled PESs. However, little detail is known about how the single PES determines reaction outcomes. Here we perform detailed experiments on HNCO photodissociation, acquiring the state-specific correlations of the NH (a1Δ) and CO (X1Σ+) products. The experiments reveal a trimodal CO rotational distribution. Dynamics simulations based on a full-dimensional machine-learning-based PES of HNCO unveil three dissociation pathways exclusively occurring on the S1 excited electronic state. One pathway, following the minimum energy path (MEP) via the transition state, contributes to mild rotational excitation in CO, while the other two pathways deviating substantially from the MEP account for relatively cold and hot CO rotational state populations. These peculiar dynamics are unambiguously governed by the S1 state PES topography, i.e., a narrow acceptance cone in the vicinity of the transition state region. The dynamical picture shown in this work will serve as a textbook example illustrating the importance of the PES topography in molecular photochemistry.

Vacuum ultraviolet photodissociation of sulfur dioxide and its implications for oxygen production in the early Earth's atmosphere.

The emergence of molecular oxygen (O2) in the Earth's primitive atmosphere is an issue of major interest. Although the biological processes leading to its accumulation in the Earth's atmosphere are well understood, its abiotic source is still not fully established. Here, we report a new direct dissociation channel yielding S(1D) + O2(a1Δg/X3Σg-) products from vacuum ultraviolet (VUV) photodissociation of SO2 in the wavelength range between 120 and 160 nm. Experimental results show O2 production to be an important channel from SO2 VUV photodissociation, with a branching ratio of 30 ± 5% at the H Lyman-α wavelength (121.6 nm). The relatively large amounts of SO2 emitted from volcanic eruptions in the Earth's late Archaean eon imply that VUV photodissociation of SO2 could have provided a crucial additional source term in the O2 budget in the Earth's primitive atmosphere. The results could also have implications for abiotic oxygen formation on other planets with atmospheres rich in volcanically outgassed SO2.

Mode specificity of water dissociating on Ni(100): An approximate full-dimensional quantum dynamics study.

The mode-specific dynamics for the dissociative chemisorption of H2O on rigid Ni(100) is investigated by approximate nine-dimensional (9D) quantum dynamics calculations. The vibrational state-specific 9D dissociation probabilities are obtained by site-averaging the site-specific seven-dimensional results based on an accurate full-dimensional potential energy surface newly developed by neural network fitting to density functional theory energy points with the revised version of the Perdew, Burke, and Ernzerhof functional. The mode specificity of H2O/Ni(100) is very different from that of H2O/Ni(111) or H2O/Cu(111) whose reactivity enhancement by vibrational excitations is quite efficient. For H2O/Ni(100), it is found that the excitation in the symmetric stretching mode is more efficacious than increasing the translational energy in promoting the reaction, while the excitations in the asymmetric stretching mode and bending mode are less efficacious than the translational energy at low collision energies. These interesting observations can be attributed to the near central-barrier reaction for H2O/Ni(100), as well as large discrepancies between the site-specific mode specificities at different impact sites. The mode-specific dynamics obtained in this study is different from that obtained with the reaction path Hamiltonian approach, indicating the importance of full-dimensional quantum dynamics for gas-surface reactions.

Full-dimensional neural network potential energy surface and dynamics of the CH2OO + H2O reaction.

An accurate global full-dimensional machine learning-based potential energy surface (PES) of the simplest Criegee intermediate (CH2OO) reaction with water monomer was developed based on the high level of extensive CCSD(T)-F12a/aug-cc-pVTZ calculations. This analytical global PES not only covers the regions of reactants to hydroxymethyl hydroperoxide (HMHP) intermediates, but also different end product channels, which facilities both the reliable and efficient kinetics and dynamics calculations. The rate coefficients calculated by the transition state theory with the interface to the full-dimensional PES agree well with the experimental results, indicating the accuracy of the current PES. Extensive quasi-classical trajectory (QCT) calculations were performed both from the bimolecular reaction CH2OO + H2O and from HMHP intermediate on the new PES. The product branching ratios of hydroxymethoxy radical (HOCH2O, HMO) + OH radical, formaldehyde (CH2O) + H2O2 and formic acid (HCOOH) + H2O were calculated. The reaction yields dominantly HMO + OH, because of the barrierless pathway from HMHP to this channel. The computed dynamical results for this product channel show the total available energy was deposited into the internal rovibrational excitation of HMO, and the energy release in OH and translational energy is limited. The large amount of OH radical found in the current study implies that the CH2OO + H2O reaction can provide crucially OH yield in Earth's atmosphere.

Full-dimensional quantum mechanical study of three-body recombination for cold 4He-4He-20Ne system.

The increase of the number of the two-body recombination channels strongly challenges the numerical calculation of the accurate rates for the three-body recombination (TBR) process and its reverse process, collision-induced dissociation (CID), at ultracold temperatures. By taking the 4He-4He-20Ne collision system as an example, we have obtained the rates for its TBR and CID processes involving all four recombination channels, including the two-body states 4He2 (l = 0) and 4He20Ne (l = 0, 1, 2) with l the rotational quantum number. By using the adiabatic hyperspherical method, we have considered not only total angular momentum J = 0 but also J > 0 in the ultracold collision energies (E = 0.01 - 100 mK × kB). It is found that 4He2 (l = 0) is the major product after the TBR process in the ultracold limit (E ≤ 0.1 mK × kB). The TBR rate into 4He2 (l = 0) is nearly one order of magnitude larger than the sum of the other three products, 4He20Ne (l = 0, 1, 2). Moreover, the CID rates for the three 4He20Ne (l = 0, 1, 2) + 4He initial states are close to each other and are smaller than that for the 4He2 (l = 0) + 20Ne initial state. Additionally, we have, for the first time, performed the channel-resolved scattering calculation that can explain the above-mentioned findings quantitatively.

A highly accurate full-dimensional ab initio potential surface for the rearrangement of methylhydroxycarbene (H3C-C-OH).

We report here a full-dimensional machine learning global potential surface (PES) for the rearrangement of methylhydroxycarbene (H3C-C-OH, 1t). The PES is trained with the fundamental invariant neural network (FI-NN) method on 91 564 ab initio energies calculated at the UCCSD(T)-F12a/cc-pVTZ level of theory, covering three possible product channels. FI-NN PES has the correct symmetry properties with respect to permutation of four identical hydrogen atoms and is suitable for dynamics studies of the 1t rearrangement. The averaged root mean square error (RMSE) is 11.4 meV. Six important reaction pathways, as well as the energies and vibrational frequencies at the stationary geometries on these pathways are accurately preproduced by our FI-NN PES. To demonstrate the capacity of the PES, we calculated the rate coefficient of hydrogen migration in -CH3 (path A) and hydrogen migration of -OH (path B) with instanton theory on this PES. Our calculations predicted the half-life of 1t to be 95 min, which is excellent in agreement with experimental observations.

Accurate fundamental invariant-neural network representation of ab initio potential energy surfaces.

Highly accurate potential energy surfaces are critically important for chemical reaction dynamics. The large number of degrees of freedom and the intricate symmetry adaption pose a big challenge to accurately representing potential energy surfaces (PESs) for polyatomic reactions. Recently, our group has made substantial progress in this direction by developing the fundamental invariant-neural network (FI-NN) approach. Here, we review these advances, demonstrating that the FI-NN approach can represent highly accurate, global, full-dimensional PESs for reactive systems with even more than 10 atoms. These multi-channel reactions typically involve many intermediates, transition states, and products. The complexity and ruggedness of this potential energy landscape present even greater challenges for full-dimensional PES representation. These PESs exhibit a high level of complexity, molecular size, and accuracy of fit. Dynamics simulations based on these PESs have unveiled intriguing and novel reaction mechanisms, providing deep insights into the intricate dynamics involved in combustion, atmospheric, and organic chemistry.

Quantum dynamics reveal different ligand effects by vibrational excitation in the dissociative chemisorption of HCl on the Au/Ag(111) surface.

The reactivity and selectivity of bimetallic surfaces are of fundamental importance in industrial applications. Here, we report the first six-dimensional (6D) quantum dynamics study for the role of surface strain and ligand effects on the reactivity of HCl on a strained pseudomorphic monolayer of Au deposited onto a Ag(111) substrate, with the aid of accurate machine learning-based potential energy surfaces. The substitute of Au into Ag changes the location of the transition state; however, the static barrier height remains roughly the same as pure Au(111). The 6D quantum dynamics calculations reveal that the surface strain due to lattice expansion slightly enhances the reactivity. The ligand effect due to electronic structure interactions between Au and Ag substantially suppresses the reactivity of HCl in the ground vibrational state but promotes the reactivity via vibrational excitation at high kinetic energies. This finding can be attributed to more close interaction with Ag atoms at the transition state close to the fcc site, as well as the tight transition-state region, making the vibrational excitation highly efficient in enhancing the reactivity. Our study quantitatively unravels the dynamical origin of reactivity control by two metals, which will ultimately provide valuable insight into the selectivity of the catalyst.

Observation of Competitive Nonadiabatic Photodissociation Dynamics of H2S+ Cations.

A comprehensive understanding of dissociation mechanisms is of fundamental importance in the photochemistry of small molecules. Here, we investigated the detailed photodissociation dynamics of H2S+ near 337 nm by using the velocity map ion imaging technique together with the theoretical characterizations by developing global full-dimensional potential energy surfaces (PESs). Rotational state resolved images were acquired for the S+(4S) + H2 product channel. Significant changes in product total kinetic energy release distributions and angular distributions have been observed within a small excitation photon energy range of 5 wavenumbers. Analysis based on the full-dimensional PESs reveals that two nonadiabatic pathways determined by the transition state connecting two minima on the 12A' state are responsible for the dramatic variation of observed product distributions. The current study has directly witnessed the competitive photodissociation mechanisms controlled by a critical energy point on the PES, thereby providing in-depth insight into the nonadiabatic dynamics in photochemistry.

Unexpected steric hindrance failure in the gas phase F- + (CH3)3CI SN2 reaction.

Base-induced elimination (E2) and bimolecular nucleophilic substitution (SN2) reactions are of significant importance in physical organic chemistry. The textbook example of the retardation of SN2 reactivity by bulky alkyl substitution is widely accepted based on the static analysis of molecular structure and steric environment. However, the direct dynamical evidence of the steric hindrance of SN2 from experiment or theory remains rare. Here, we report an unprecedented full-dimensional (39-dimensional) machine learning-based potential energy surface for the 15-atom F- + (CH3)3CI reaction, facilitating the reliable and efficient reaction dynamics simulations that can reproduce well the experimental outcomes and examine associated atomic-molecular level mechanisms. Moreover, we found surprisingly high "intrinsic" reactivity of SN2 when the E2 pathway is completely blocked, indicating the reaction that intends to proceed via E2 transits to SN2 instead, due to a shared pre-reaction minimum. This finding indicates that the competing factor of E2 but not the steric hindrance determines the small reactivity of SN2 for the F- + (CH3)3CI reaction. Our study provides new insight into the dynamical origin that determines the intrinsic reactivity in gas-phase organic chemistry.

Dynamical Effects of SN2 Reactivity Suppression by Microsolvation: Dynamics Simulations of the F-(H2O) + CH3I Reaction on a 21-Dimensional Potential Energy Surface.

A comparison of atomistic dynamics between microsolvated and unsolvated reactions can expose the precise role of solvent molecules and thus provide deep insight into how solvation influences chemical reactions. Here we developed the first full-dimensional analytical potential energy surface of the F-(H2O) + CH3I reaction, which facilitates the efficient dynamics simulations on a quantitatively accurate level. The computed SN2 reactivity suppression ratio of the monosolvated F-(H2O) + CH3I reaction relative to the unsolvated F- + CH3I reaction as a function of collision energy first increases and then decreases steadily, forming an inverted-V shape, due to the combined dynamical effects of interaction time, steric hindrance, and collision-induced dehydration. Moreover, further analysis reveals that the steric effect of the F-(H2O) + CH3I reaction resulting from the single water molecule is manifested mainly in dragging the F- anion away from the central C atom, rather than shielding F- from C. Our study shows there is great potential in rigorously studying the role of the solvent in more complicated reactions.

Double-Roaming Dynamics in the H + C2H2 → H2 + C2H Reaction: Acetylene-Facilitated Roaming and Vinylidene-Facilitated Roaming.

We report two novel roaming pathways for the H + C2H2 → H2 + C2H reaction by performing extensive quasiclassical trajectory calculations on a new, global, high-level machine learning-based potential energy surface. One corresponds to the acetylene-facilitated roaming pathway, where the H atom turns back from the acetylene + H channel and abstracts another H atom from acetylene. The other is the vinylidene-facilitated roaming, where the H atom turns back from the vinylidene + H channel and abstracts another H from vinylidene. The "double-roaming" pathways account for roughly 95% of the total cross section of the H2 + C2H products at the collision energy of 70 kcal/mol. These computational results give valuable insights into the significance of the two isomers (acetylene and vinylidene) in chemical reaction dynamics and also the experimental search for roaming dynamics in this bimolecular reaction.

Neural Network Representation of Three-State Quasidiabatic Hamiltonians Based on the Transformation Properties from a Valence Bond Model: Three Singlet States of H3.

A neural network (NN) approach was recently developed to construct accurate quasidiabatic Hamiltonians for two-state systems with conical intersections. Here, we derive the transformation properties of elements of 3 × 3 quasidiabatic Hamiltonians based on a valence bond (VB) model and extend the NN-based method to accurately diabatize the three lowest electronic singlet states of H3+, which exhibit the avoided crossing between the ground and first excited states and the conical intersection between the first and second excited states for equilateral triangle configurations (D3h). The current NN framework uses fundamental invariants (FIs) as the input vector and appropriate symmetry-adapted functions called covariant basis to account for the special symmetry of complete nuclear permutational inversion (CNPI). The resulting diabatic potential energy matrix (DPEM) can reproduce the ab initio adiabatic energies, energy gradients, and derivative couplings between adjacent states as well as the particular symmetry. The accuracy of DPEM is further validated by full-dimensional quantum dynamics calculations. The flexibility of the FI-NN approach based on the VB model shows great potential to resolve diabatization problems for many extended and multistate systems.