Mode-specific Dynamics Research Articles

The quasi-classical trajectory study of vibrational mode-specific dynamics of the multi-channel reaction OH− + CH3F

The vibrational mode-specific dynamics of the multiple channel reaction, OH− + CH3F, namely the effects of excitations of the CF stretching (v1), CH3 rocking (v3), CH3 umbrella (v4), CH3 deformation (v5), CH symmetric stretching (v7) and CH asymmetric stretching (v8) as well as the OH stretching (vOH) on the reactivity of different product channels, were investigated by running extensive quasi-classical trajectories on a latest accurate full-dimensional potential energy surface. Integral cross sections (ICS), differential cross sections (DCS), product state populations, and product energy distributions for different vibrational excitation modes were calculated and analyzed. The Sudden Vector Projection model is also employed to rationalize these dynamic results.

Vibrational mode-specificity in the dynamics of the OH- + CH3I multi-channel reaction.

We report a comprehensive characterization of the vibrational mode-specific dynamics of the OH- + CH3I reaction. Quasi-classical trajectory simulations are performed at four different collision energies on our previously-developed full-dimensional high-level abinitio potential energy surface in order to examine the impact of four different normal-mode excitations in the reactants. Considering the 11 possible pathways of OH- + CH3I, pronounced mode-specificity is observed in reactivity: In general, the excitations of the OH- stretching and CH stretching exert the greatest influence on the channels. For the SN2 and proton-abstraction products, the reactant initial attack angle and the product scattering angle distributions do not show major mode-specific features, except for SN2 at higher collision energies, where forward scattering is promoted by the CI stretching and CH stretching excitations. The post-reaction energy flow is also examined for SN2 and proton abstraction, and it is unveiled that the excess vibrational excitation energies rather transfer into the product vibrational energy because the translational and rotational energy distributions of the products do not represent significant mode-specificity. Moreover, in the course of proton abstraction, the surplus vibrational energy in the OH- reactant mostly remains in the H2O product owing to the prevailing dominance of the direct stripping mechanism.

First-principles mode-specific reaction dynamics.

Controlling the outcome of chemical reactions by exciting specific vibrational and/or rotational modes of the reactants is one of the major goals of modern reaction dynamics studies. In the present Perspective, we focus on first-principles vibrational and rotational mode-specific dynamics computations on reactions of neutral and anionic systems beyond six atoms such as X + C2H6 [X = F, Cl, OH], HX + C2H5 [X = Br, I], OH- + CH3I, and F- + CH3CH2Cl. The dynamics simulations utilize high-level ab initio analytical potential energy surfaces and the quasi-classical trajectory method. Besides initial state specificity and the validity of the Polanyi rules, mode-specific vibrational-state assignment for polyatomic product species using normal-mode analysis and Gaussian binning is also discussed and compared with experiment.

Vibrational Mode-Specific Dynamics of the OH + C2H6 Reaction.

We investigate the effects of the initial vibrational excitations on the dynamics of the OH + C2H6 → H2O + C2H5 reaction using the quasi-classical trajectory method and a full-dimensional analytical ab initio potential energy surface. Excitation of the initial CH, CC, and OH stretching modes enhances, slightly inhibits, and does not affect the reactivity, respectively. Translational energy activates the early-barrier title reaction more efficiently than OH and CC stretching excitations, in accord with the Polanyi rules whereas CH stretching modes have similar or higher efficacy than translation, showing that these rules are not always valid in polyatomic processes. Scattering angle, initial attack angle, and product translational energy distributions show the dominance of direct stripping with increasing collision energy, side-on OH and isotropic C2H6 attack preferences, and substantial reactant-product translational energy transfer without any significant mode specificity. The reactant vibrational excitation energy of OH and C2H6 flows into the H2O and C2H5 product vibrations, respectively, whereas product rotations are not affected. The computed mode-specific H2O vibrational distributions show that initial OH excitation appears in the asymmetric stretching vibration of the H2O product and allow comparison with experiments.

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.

Dynamics of Dissociative Chemisorption of NH3 on Fe(111) on a Twelve-Dimensional Potential Energy Surface

We constructed a new, accurate twelve-dimensional potential energy surface (PES) for ammonia dissociative chemisorption (DC) on a rigid Fe(111) surface using the fundamental invariant-neural network fitting to a large number of density functional theory data points. The DC dynamics simulations were carried out by the quasi-classical trajectory (QCT) approach. At very low collision energies, the molecules experienced a large number of rebounds due to the deep pre-transition-state adsorption well and finally decomposed around the global transition state. At high collision energies, the bridge site with a loose transition state was the most favorable site for dissociation. The mode-specific dynamics revealed that excitations in symmetric stretch and umbrella modes were most efficient in promoting the dissociation and were more efficacious than the same amount of translational energy. The computed large dissociation probability for NH3/Fe(111) supported the fact that iron is an effective catalyst for ammonia dissociation, which is of practical importance in producing clean hydrogen.

Mode specific dynamics for the acoustic vibrations of a gold nanoplate

The vibrational modes of semiconductor and metal nanostructures occur in the MHz to GHz frequency range, depending on dimensions. These modes are at the heart of nano-optomechanical devices, and understanding how they dissipate energy is important for applications of the devices. In this paper ultrafast transient absorption microscopy has been used to examine the breathing modes of a single gold nanoplate, where up to four overtones were observed. Analysis of the frequencies and amplitudes of the modes using a simple continuum mechanics model shows that the system behaves as a free plate, even though it is deposited onto a surface with no special preparation. The overtones decay faster than the fundamental mode, which is not predicted by continuum mechanics calculations of mode damping due to radiation of sound waves. Possible reasons for this effect include frequency dependent thermoelastic effects in the nanoplate, and/or flow of acoustic energy out of the excitation region.

Theoretical vibrational mode-specific dynamics studies for the HBr + C2H5 reaction.

A quasi-classical trajectory (QCT) study is performed for the HBr + C2H5 multi-channel reaction using a recently-developed high-level ab initio full-dimensional spin-orbit-corrected potential energy surface (PES) by exciting five different vibrational modes of reactants at five collision energies. The effect of the normal-mode excitations on the reactivity, the mechanism, and the post-reaction energy flow is followed. A significant decrease of the reactivity caused by the longer initial distances of the reactants for the vHBr = 1 reaction at low collision energy (Ecoll) is observed due to the intramolecular vibrational-energy redistribution and the classical nature of the QCT method. All of the three reaction pathways (H-abstraction, Br-abstraction, and H-exchange) are intensely promoted when the HBr-stretching mode is excited. No clear promotion is observed when excitation is imposed to C2H5 except that asymmetric CH-stretching helps the H-exchange process. The enhancement effect of the excitation in the HBr vibrational mode is found to be much more effective than increasing the translational energy, in contrast to the HBr + CH3 reaction. The forward scattering mechanism can be clearly promoted by the excitation of the HBr-stretching mode, or by the high collision energy, indicating the dominance of the direct stripping mechanism in these cases. At low collision energy with no excitation or excitation of any vibrational mode of C2H5, the forward scattering feature is less obvious. At Ecoll = 1 kcal mol-1, when HBr-stretching is excited, the product clearly gains more relative translational energy. However, it is interesting to see that when the excitation is in C2H5, the effect is the opposite, i.e., the product gains less relative translational energy compared to the ground-state reaction.

Vibrational mode-specific quasi-classical trajectory studies for the two-channel HI + C2H5 reaction.

We report a detailed dynamics study on the mode-specificity of the HI + C2H5 two-channel reaction (H-abstraction and I-abstraction), through performing quasi-classical trajectory computations on a recently developed high-level ab initio full-dimensional spin-orbit-corrected potential energy surface, by exciting four different vibrational modes of reactants at five collision energies. The effect of the normal-mode excitations on the reactivity, the mechanism, and the post-reaction energy flow is investigated. Both reaction pathways are intensely promoted when the HI-stretching mode is excited while the excitations imposed on C2H5 somewhat surprisingly inhibit the dominant H-abstraction reaction pathway. The enhancement effect of the excitation in the HI vibrational mode is found to be much more effective than increasing the translational energy, similar to the HBr + C2H5 reaction. Not like the Br-abstraction pathway, however, the I-abstraction reaction pathway could be comparable to the dominant H-abstraction reaction pathway. The dominance of the direct stripping mechanism is indicated in H-abstraction while the direct rebound mechanism is observed in I-abstraction. The H-abstraction is much pickier about the initial attack angle distributions for HI than I-abstraction is, which leads to a decrease in reactivity in the H-abstraction reaction pathway. The dominance of side-on CH3CH2 attack in I-abstraction is more obvious than in the case of H-abstraction. In the case of the H-abstraction reaction pathway, the major part of the initial translational energy ends up in translational recoil, while for I-abstraction most energy excites the product C2H5I.

Effects of vibrational and rotational excitations on dissociative chemisorption dynamics of N2 on Fe(111)

The dissociative chemisorption of N2 is the rate-limiting step for ammonia synthesis in industry. Here, we investigated the role of initially vibrational excitation and rotational excitation of N2 for its reactivity on the Fe(111) surface, based on a recently developed six-dimensional potential energy surface. Six-dimensional quantum dynamics study was carried out to investigate the effect of vibrational excitation for incidence energy below 1.6 eV, due to significant quantum effects for this reaction. The effects of vibrational and rotational excitations at high incidence energies were revealed by quasiclassical trajectory calculations. We found that raising the translational energy can enhance the dissociation probability to some extent, however, the vibrational excitation or rotational excitation can promote dissociation more efficiently than the same amount of translational energy. This study provides valuable insight into the mode-specific dynamics of this heavy diatom-surface reaction.

A parametric and feasibility study for data sampling of the dynamic mode decomposition: range, resolution, and universal convergence states

Scientific research and engineering practice often require the modeling and decomposition of nonlinear systems. The dynamic mode decomposition (DMD) is a novel Koopman-based technique that effectively dissects high-dimensional nonlinear systems into periodically distinct constituents on reduced-order subspaces. As a novel mathematical hatchling, the DMD bears vast potentials yet an equal degree of unknown. This effort investigates the nuances of DMD sampling with an engineering-oriented emphasis. It aimed at elucidating how sampling range and resolution affect the convergence of DMD modes. We employed the most classical nonlinear system in fluid mechanics as the test subject—the turbulent free-shear flow over a prism—for optimal pertinency. We numerically simulated the flow by the dynamic-stress Large-Eddies Simulation with Near-Wall Resolution. With the large-quantity, high-fidelity data, we parametrized and identified four global convergence states: Initialization, Transition, Stabilization, and Divergence with increasing sampling range. Results showed that Stabilization is the optimal state for modal convergence, in which DMD output becomes independent of the sampling range. The Initialization state also yields sufficient accuracy for most system reconstruction tasks. Moreover, defying popular beliefs, over-sampling causes algorithmic instability: as the temporal dimension, n, approaches and transcends the spatial dimension, m (i.e., m < n), the output diverges and becomes meaningless. Additionally, the convergence of the sampling resolution depends on the mode-specific dynamics, such that the resolution of 15 frames per cycle for target activities is suggested for most engineering implementations. Finally, a bi-parametric study revealed that the convergence of the sampling range and resolution are mutually independent.

Mode specificity dynamics of prototypical multi-channel H+CH3OH reaction on globally accurate potential energy surface

The H+CH3OH reaction, which plays an important role in combustion and the interstellar medium, presents a prototypical system with multiple channels. In this work, mode specific dynamics of different product channels is investigated theoretically on a recently developed reliable potential energy surface based on a large number of data points calculated at the level of UCCSD(T)-F12a/AVTZ. It has been demonstrated that vibrational excitations of the O-H stretching motion, the torsional motion, the C-H stretching vibrations, show different influences on the four product channels, H2+CH3O, H2+CH2OH, H2O+CH3, and H+CH3OH. This work is helpful for understanding the mode-specific dynamics and controlling the competition for complicated reactions with multiple product channels.

Vibrational mode-specific dynamics of the F- + CH3CH2Cl multi-channel reaction.

We investigate the mode-specific dynamics of the ground-state, C-Cl stretching (v10), CH2 wagging (v7), sym-CH2 stretching (v1), and sym-CH3 stretching (v3) excited F- + CH3CH2Cl(vk = 0, 1) [k = 10, 7, 1, 3] → Cl- + CH3CH2F (SN2), HF + CH3CHCl-, FH⋯Cl- + C2H4, and Cl- + HF + C2H4 (E2) reactions using a full-dimensional high-level analytical global potential energy surface and the quasi-classical trajectory method. Excitation of the C-Cl stretching, CH2 stretching, and CH2/CH3 stretching modes enhances the SN2, proton abstraction, and FH⋯Cl- and E2 channels, respectively. Anti-E2 dominates over syn-E2 (kinetic anti-E2 preference) and the thermodynamically-favored SN2 (wider reactive anti-E2 attack angle range). The direct (a) SN2, (b) proton abstraction, (c) FH⋯Cl- + C2H4, (d) syn-E2, and (e) anti-E2 channels proceed with (a) back-side/backward, (b) isotropic/forward, (c) side-on/forward, (d) front-side/forward, and (e) back-side/forward attack/scattering, respectively. The HF products are vibrationally cold, especially for proton abstraction, and their rotational excitation increases for proton abstraction, anti-E2, and syn-E2, in order. Product internal-energy and mode-specific vibrational distributions show that CH3CH2F is internally hot with significant C-F stretching and CH2 wagging excitations, whereas C2H4 is colder. One-dimensional Gaussian binning technique is proved to solve the normal mode analysis failure caused by methyl internal rotation.

Vibrational mode-specific dynamics of the F(2P3/2) + C2H6 → HF + C2H5 reaction.

We investigate the competing effect of vibrational and translational excitation and the validity of the Polanyi rules in the early- and negative-barrier F(2P3/2) + C2H6 → HF + C2H5 reaction by performing quasi-classical dynamics simulations on a recently developed full-dimensional multi-reference analytical potential energy surface. The effect of five normal-mode excitations of ethane on the reactivity, the mechanism, and the post-reaction energy flow is followed through a wide range of collision energies. Promoting effects of vibrational excitations and interaction time, related to the slightly submerged barrier, are found to be suppressed by the early-barrier-induced translational enhancement, in contrast to the slightly late-barrier Cl + C2H6 reaction. The excess vibrational energy mostly converts into ethyl internal excitation while collision energy is transformed into product separation. The substantial reaction energy excites the HF vibration, which tends to show mode-specificity and translational energy dependence as well. With increasing collision energy, direct stripping becomes dominant over the direct rebound and indirect mechanisms, being basically independent of reactant excitation.

Mode-specific quantum dynamics and kinetics of the hydrogen abstraction reaction OH + H2O → H2O + OH.

Hydrogen abstraction processes are prevalent in a wide range of chemically active environments. In this work, the prototypical hydrogen exchange reaction OH + H2O → H2O + OH is investigated on an accurate ab initio based potential energy surface using an initial state-selected time-dependent wave packet method. Exciting either the symmetric stretching mode or the antisymmetric stretching mode of the reactant H2O promotes the reaction more than exciting the bending mode. The vibrational energy initially deposited in H2O is more efficient than the translational energy in promoting the reaction. There exists a remarkable synergistic effect between the stretching mode and the bending mode as the efficacy for the combination band excitation is larger than the sum of individual excitations. The mode-specific dynamics is partially rationalized by the sudden vector projection model. Besides, the mode-specific rate constants apparently exhibit a strong non-Arrhenius behavior at low and moderate temperatures.

Mode specific dynamics in bond selective reaction O'(3P) + HOD → O'H + OD/O'D + OH.

Taking advantage of bond selectivity and mode specificity has long been realized to control the outcome of chemical reactions. The mode-specific dynamics in the bond selective abstraction reaction O'(3P) + HOD are investigated using a full-dimensional time-dependent quantum wave packet method. Integral cross sections and product branching ratios from several low-lying vibrational states of the reactant HOD are calculated on an accurate global potential energy surface describing the lowest triplet state of the HOOH system. Both the H-abstraction reaction and the D-abstraction reaction prefer the vibrational energy to the translational energy, satisfying the prediction of Polanyi rules for a late-barrier reaction. The observed strong bond selectivity can be rationalized by the sudden vector projection model as well. The bias to the D-abstraction channel for the reaction O'(3P) + HOD from the reactant ground state can be partially attributed to the different mass combination in comparison to the H + HOD reaction, in which the H-abstraction channel is more favored.

State-Resolved Metal Nanoparticle Dynamics Viewed through the Combined Lenses of Ultrafast and Magneto-optical Spectroscopies.

Electronic carrier dynamics play pivotal roles in the functional properties of nanomaterials. For colloidal metals, the mechanisms and influences of these dynamics are structure dependent. The coherent carrier dynamics of collective plasmon modes for nanoparticles (approximately 2 nm and larger) determine optical amplification factors that are important to applied spectroscopy techniques. In the nanocluster domain (sub-2 nm), carrier coupling to vibrational modes affects photoluminescence yields. The performance of photocatalytic materials featuring both nanoparticles and nanoclusters also depends on the relaxation dynamics of nonequilibrium charge carriers. The challenges for developing comprehensive descriptions of carrier dynamics spanning both domains are multifold. Plasmon coherences are short-lived, persisting for only tens of femtoseconds. Nanoclusters exhibit discrete carrier dynamics that can persist for microseconds in some cases. On this time scale, many state-dependent processes, including vibrational relaxation, charge transfer, and spin conversion, affect carrier dynamics in ways that are nonscalable but, rather, structure specific. Hence, state-resolved spectroscopy methods are needed for understanding carrier dynamics in the nanocluster domain. Based on these considerations, a detailed understanding of structure-dependent carrier dynamics across length scales requires an appropriate combination of spectroscopic methods. Plasmon mode-specific dynamics can be obtained through ultrafast correlated light and electron microscopy (UCLEM), which pairs interferometric nonlinear optical (INLO) with electron imaging methods. INLO yields nanostructure spectral resonance responses, which capture the system's homogeneous line width and coherence dynamics. State-resolved nanocluster dynamics can be obtained by pairing ultrafast with magnetic-optical spectroscopy methods. In particular, variable-temperature variable-field (VTVH) spectroscopies allow quantification of transient, excited states, providing quantification of important parameters such as spin and orbital angular momenta as well as the energy gaps that separate electronic fine structure states. Ultrafast two-dimensional electronic spectroscopy (2DES) can be used to understand how these details influence state-to-state carrier dynamics. In combination, VTVH and 2DES methods can provide chemists with detailed information regarding the structure-dependent and state-specific flow of energy through metal nanoclusters. In this Account, we highlight recent advances toward understanding structure-dependent carrier dynamics for metals spanning the sub-nanometer to tens of nanometers length scale. We demonstrate the use of UCLEM methods for arresting interband scattering effects. For sub-nanometer thiol-protected nanoclusters, we discuss the effectiveness of VTVH for distinguishing state-specific radiative recombination originating from a gold core versus organometallic protecting layers. This state specificity is refined further using femtosecond 2DES and two-color methods to isolate so-called superatom state dynamics and vibrationally mediated spin-conversion and emission processes. Finally, we discuss prospects for merging VTVH and 2DES methods into a single platform.

Understanding mode-specific dynamics in the local mode representation.

Mode specificity is a main characteristic of transition state control of reaction dynamics. The normal mode representation has been widely employed to describe the mode specificity in elementary chemical reactions. However, spectroscopists have demonstrated that the local mode representation has advantages in analyzing the overtone and combination band spectra. In this work, the mode-specific reaction dynamics between the hydrogen atom and the molecules H2S and H2O is studied using a full-dimensional quantum scattering model in the (2 + 1) Radau-Jacobi coordinates. The mode specificities in the reactions that violates our physical intuition in the normal mode representation are well rationalized in the local mode representation. The energy flow between different XH bonds resulting from the intramolecular interaction and/or intermolecular interaction is unveiled, together with its impacts on dynamics of the abstraction and exchange reactions.

Mode specificity for the dissociative chemisorption of H2O on Cu(111): a quantum dynamics study on an accurately fitted potential energy surface.

The mode-specific dynamics for the dissociative chemisorption of H2O on Cu(111) is first investigated by seven-dimensional quantum dynamics calculations, based on an accurately fitted potential energy surface (PES) recently developed by neural network fitting to DFT energy points. It is indicated that excitations in all three vibrational modes have a significant impact on reactivity, which are more efficacious than increasing the translational energy in promoting the reaction, with the largest enhancement for the excitation in the asymmetric stretching mode. There is large discrepancy between the six-dimensional reactivities with fixed azimuthal angles and seven-dimensional results, revealing that the 6D "flat surface" model cannot accurately characterize the reaction dynamics. The azimuthal angle-averaging approach is validated for vibrational excited states of the reactant, where the 7D mode-specific probability can be well reproduced by averaging the 6D azimuthal angle-fixed probabilities over 18 angles.

Mode specific dynamics of the H2 + CH3 → H + CH4 reaction studied using quasi-classical trajectory and eight-dimensional quantum dynamics methods

An eight-dimensional quantum dynamical model is proposed and applied to the title reaction. The reaction probabilities and integral cross sections have been determined for both the ground and excited vibrational states of the two reactants. The results indicate that the H2 stretching and CH3 umbrella modes, along with the translational energy, strongly promote the reactivity, while the CH3 symmetric stretching mode has a negligible effect. The observed mode specificity is confirmed by full-dimensional quasi-classical trajectory calculations. The mode specificity can be interpreted by the recently proposed sudden vector projection model, which attributes the enhancement effects of the reactant modes to their strong couplings with the reaction coordinate at the transition state.