Dynamics of the Cl + CH3CN reaction on an automatically-developed full-dimensional ab initio potential energy surface.

A full-dimensional analytical potential energy surface (PES) is developed for the Cl + CH3CN reaction following our previous work on the benchmark ab initio characterization of the stationary points. The spin-orbit-corrected PES is constructed using the Robosurfer program and a fifth-order permutationally invariant polynomial method for fitting the high-accuracy energy points determined by a ManyHF-based coupled-cluster/triple-zeta-quality composite method. Quasi-classical trajectory simulations are performed at six collision energies between 10 and 60 kcal mol-1. Multiple low-probability product channels are found, including isomerization to isonitrile (CH3NC), but out of the eight possible channels, only the H-abstraction has significant reaction probability; thus, detailed dynamics studies are carried out only for this reaction. The cross sections and opacity functions show that the probability of the H-abstraction reaction increases with increasing collision energy (Ecoll). Scattering angle, initial attack angle, and product relative translational energy distributions indicate that the mechanism changes with the collision energy from indirect/rebound to direct stripping. The distribution of initial attack angles shows a clear preference for methyl group attack but with different angles at different Ecoll values. Post-reaction energy distributions show that the energy transfer is biased toward the products' relative translational energy instead of their internal energy. Rotational and vibrational energy have about the same amount of contribution to the internal energy in the case of both products (HCl and CH2CN), i.e., both of them are formed with high rotational excitations. HCl is produced mostly in the ground vibrational state, while a notable fraction of CH2CN is formed with vibrational excitation.

Revealing new pathways for the reaction of Criegee intermediate CH2OO with SO2.

Criegee intermediates play an important role in the tropospheric oxidation models through their reactions with atmospheric trace chemicals. We develop a global full-dimensional potential energy surface for the CH2OO + SO2 system and reveal how the reaction happens step by step by quasi-classical trajectory simulations. A new pathway forming the main products (CH2O + SO3) and a new product channel (CO2 + H2 + SO2) are predicted in our simulations. The new pathway appears at collision energies greater than 10 kcal/mol whose behavior demonstrates a typical barrier-controlled reaction. This threshold is also consistent with the ab initio transition state barrier height. For the minor products, a loose complex OCH2O ∙ ∙ ∙ SO2 is formed first, and then in most cases it soon turns into HCOOH + SO2, in a few cases it decomposes into CO2 + H2 + SO2 which is a new product channel, and rarely it remains as ∙OCH2O ∙ + SO2.

Benchmark ab initio characterization of the multi-channel Cl + CH3X [X = F, Cl, Br, I] reactive potential energy surfaces.

We determine benchmark geometries and relative energies for the stationary points of the Cl + CH3X [X = F, Cl, Br, I] reactions. We consider four possible reaction pathways: hydrogen abstraction, hydrogen substitution, halogen abstraction, and halogen substitution, where the substitution processes can proceed via either Walden inversion or front-side attack. We perform geometry optimizations and obtain harmonic vibrational frequencies at the explicitly-correlated UCCSD(T)-F12b/aug-cc-pVTZ level of theory, followed by UCCSD(T)-F12b/aug-cc-pVQZ single-point computations to make finite-basis-set error negligible. To reach chemical (<1 kcal mol-1), or even subchemical (<0.5 kcal mol-1) accuracy, we include core-correlation, scalar relativistic, post-(T), spin-orbit-splitting and zero-point-energy contributions, as well, in the relative energies of all the stationary points. Our benchmark 0 K reaction enthalpies are compared to available experimental results and show good agreement. The stationary-point structures and energetics are interpreted in terms of Hammond's postulate and used to make predictions related to the dynamical behavior of these reactive systems.

High-level analytical potential-energy-surface-based dynamics of the OH- + CH3CH2Cl SN2 and E2 reactions in full (24) dimensions.

We develop a coupled-cluster full-dimensional global potential energy surface (PES) for the OH- + CH3CH2Cl reactive system, using the Robosurfer program package, which automatically samples configurations along PES-based trajectories as well as performs ab initio computations with Molpro and fitting with the monomial symmetrization approach. The analytical PES accurately describes both the bimolecular nucleophilic substitution (SN2) and elimination (E2) channels leading to the Cl- + CH3CH2OH and Cl- + H2O + C2H4 products, respectively, and allows efficient quasi-classical trajectory (QCT) simulations. QCT computations on the new PES provide accurate statistically-converged integral and differential cross sections for the OH- + CH3CH2Cl reaction, revealing the competing dynamics and mechanisms of the SN2 and E2 (anti, syn, ß-α transfer) channels as well as various additional pathways leading to induced inversion of the CH3CH2Cl reactant, H-exchange between the reactants, H2O⋯Cl- complex formation, and H2O + CH3CHCl- products via proton abstraction.

Benchmark ab initio characterization of the complex potential energy surfaces of the HOO- + CH3Y [Y = F, Cl, Br, I] reactions.

The α-effect is a well-known phenomenon in organic chemistry, and is related to the enhanced reactivity of nucleophiles involving one or more lone-pair electrons adjacent to the nucleophilic center. The gas-phase bimolecular nucleophilic substitution (SN2) reactions of α-nucleophile HOO- with methyl halides have been thoroughly investigated experimentally and theoretically; however, these investigations have mainly focused on identifying and characterizing the α-effect of HOO-. Here, we perform the first comprehensive high-level ab initio mapping for the HOO- + CH3Y [Y = F, Cl, Br and I] reactions utilizing the modern explicitly-correlated CCSD(T)-F12b method with the aug-cc-pVnZ [n = 2-4] basis sets. The present ab initio characterization considers five distinct product channels of SN2: (CH3OOH + Y-), proton abstraction (CH2Y- + H2O2), peroxide ion substitution (CH3OO- + HY), SN2-induced elimination (CH2O + HY + HO-) and SN2-induced rearrangement (CH2(OH)O- + HY). Moreover, besides the traditional back-side attack Walden inversion, the pathways of front-side attack, double inversion and halogen-bond complex formation have also been explored for SN2. With regard to the Walden inversion of HOO- + CH3Cl, the previously unaddressed discrepancies concerning the geometry of the corresponding transition state are clarified. For the HOO- + CH3F reaction, the recently identified SN2-induced elimination is found to be more exothermic than the SN2 channel, submerged by ∼36 kcal mol-1. The accuracy of our high-level ab initio calculations performed in the present study is validated by the fact that our new benchmark 0 K reaction enthalpies show excellent agreement with the experimental data in nearly all cases.

Dynamics of the HCl + C2H5 Multichannel Reaction on a Full-Dimensional Ab Initio Potential Energy Surface.

We report a full-dimensional ab initio analytical potential energy surface (PES), which accurately describes the HCl + C2H5 multichannel reaction. The new PES is developed by iteratively adding selected configurations along HCl + C2H5 quasi-classical trajectories (QCTs), thereby improving our previous Cl(2P3/2) + C2H6 PES using the Robosurfer program package. QCT simulations for the H'Cl + C2H5 reaction reveal hydrogen-abstraction, chlorine-abstraction, and hydrogen-exchange channels leading to Cl + C2H5H', H' + C2H5Cl, and HCl + C2H4H', respectively. Hydrogen abstraction dominates in the collision energy (Ecoll) range of 1-80 kcal/mol and proceeds with indirect isotropic scattering at low Ecoll and forward-scattered direct stripping at high Ecoll. Chlorine abstraction opens around 40 kcal/mol collision energy and becomes competitive with hydrogen abstraction at Ecoll = 80 kcal/mol. A restricted opening of the cone of acceptance in the Cl-abstraction reaction is found to result in the preference for a backward-scattering direct-rebound mechanism at all energies studied. Initial attack-angle distributions show mainly side-on collision preference of C2H5 for both abstraction reactions, and in the case of the HCl reactant, H/Cl-side preference for the H/Cl abstraction. For hydrogen abstraction, the collision energy transfer into the product translational and internal energy is almost equally significant, whereas in the case of chlorine abstraction, most of the available energy goes into the internal degrees of freedom. Hydrogen exchange is a minor channel with nearly constant reactivity in the Ecoll range of 10-80 kcal/mol.

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.

Imaging the Ion-Molecule Reaction Dynamics of O- + CD4.

While neutral reactions involved in methane oxidation have been intensively studied, much less information is known about the reaction dynamics of the oxygen radical anion with methane. Here, we study the scattering dynamics of this anion-molecule reaction using crossed-beam velocity map imaging with deuterated methane. Differential scattering cross sections for the deuterium abstraction channel have been determined at relative collision energies between 0.2 and 1.5 eV and ab initio calculations of the important stationary points along the reaction pathway have been performed. At lower collision energies, direct backscattering and indirect complex-mediated reaction dynamics are observed, whereas at higher energies, sideways deuterium stripping dominates the reaction. Above 0.7 eV collision energy, a suppressed cross section is observed at low product ion velocities, which is likely caused by the endoergic pathway of combined deuteron/deuterium transfer, forming heavy water. The measured product internal energy is attributed mainly to the low-lying deformation and out-of-plane bending vibrations of the methyl radical product. The results are compared with a previous crossed-beam result for the reaction of oxygen anions with nondeuterated ̧methane and with the related neutral-neutral reactions, showing similar dynamics and qualitative agreement.

Detailed quasiclassical dynamics of the F- + SiH3Cl multi-channel reaction.

We report a detailed quasiclassical trajectory study on the F- + SiH3Cl multi-channel reaction using a full-dimensional ab initio analytical potential energy surface. Reaction probabilities, cross sections, initial attack and scattering angle distributions as well as product relative translational, internal, vibrational, and rotational energy distributions are obtained in the collision energy range of 1-40 kcal mol-1 for the following channels: SiH3F + Cl-, SiH2Cl- + HF, SiH2F- + HCl, SiH2FCl + H-, SiH2 + FHCl-, and SiHFCl- + H2. All the channels are translationally cold indicating indirect mechanisms, except proton transfer (SiH2Cl- + HF), which shows mixed direct-indirect character. The angular distributions vary depending on collision energy and inversion/retention for SiH3F + Cl-. In the case of SiH2Cl- + HF front-side/back-side attack backward-forward/forward scattering preference is found at low/high collision energy. SiH2F- + HCl is formed with isotropic scattering and the preferred angle of attack is similar to the SiH3F + Cl- channel. SiH2FCl + H-/SiH2 + FHCl- favors back-side attack and isotropic/backward scattering, whereas SiHFCl- + H2 does not show significant angular preference.

Automated potential energy surface development and comprehensive dynamics for the F + CH3NH2 reaction.

This work is an extensive investigation of the F + CH3NH2 reaction dynamics using a newly-developed potential energy surface (PES). The full-dimensional spin-orbit (SO) corrected (MRCI+Q/aug-cc-pwCVDZ) PES is developed by the Robosurfer program package and the ManyHF method is used in order to fix the Hartree-Fock (HF) convergence issues in the entrance channel. On the surface, retrieved by the fitting of the iteratively extended set of the ManyHF-CCSD(T)-F12a/triple-zeta-quality and SO-corrected energy points, quasi-classical trajectory (QCT) simulations are run. By analyzing the opacity functions and integral cross sections (ICSs) of six reaction channels, the dynamics of the two most reactive hydrogen-abstraction reactions resulting in HF + CH2NH2/CH3NH products are selected for a thorough examination. Despite the statistically and thermodynamically expected results, the kinetically preferred amino hydrogen-abstraction is the dominant mechanism at low collision energies. The initial attack angle and scattering angle distributions are investigated as well. The post-reaction energy distributions show that the collision energy mostly converts into the translational energy of the products, while the reaction energy excites the vibration of the products. The computed vibrationally resolved rotational distributions and vibrational state distributions of the HF product are compared to experimental data, and the theory and experiment are found to be in good agreement.

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 ab initio 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.

Phosphorus-centered ion-molecule reactions: benchmark ab initio characterization of the potential energy surfaces of the X- + PH2Y [X, Y = F, Cl, Br, I] systems.

In the present work we determine the benchmark relative energies and geometries of all the relevant stationary points of the X- + PH2Y [X, Y = F, Cl, Br, I] identity and non-identity reactions using state-of-the-art electronic-structure methods. These phosphorus-centered ion-molecule reactions follow two main reaction routes: bimolecular nucleophilic substitution (SN2), leading to Y- + PH2X, and proton transfer, resulting in HX + PHY- products. The SN2 route can proceed through Walden-inversion, front-side-attack retention, and double-/multiple-inversion pathways. In addition, we also identify the following product channels: H--formation, PH2-- and PH2-formation, 1PH- and 3PH-formation, H2-formation and HY + PHX- formation. The benchmark classical relative energies are obtained by taking into account the core-correlation, scalar relativistic, and post-(T) corrections, which turn out to be necessary to reach subchemical (<1 kcal mol-1) accuracy of the results. Classical relative energies are augmented with zero-point-energy contributions to gain the benchmark adiabatic energies.

Full-dimensional automated potential energy surface development and detailed dynamics for the CH2OO + NH3 reaction.

With the help of the ROBOSURFER program package, a global full-dimensional potential energy surface (PES) for the reaction of the Criegee intermediate, CH2OO, with the NH3 molecule is developed iteratively using different ab initio methods and the monomial symmetrization fitting approach. The final permutationally-invariant analytical PES is constructed based on 23447 geometries and the corresponding ManyHF-based CCSD(T)-F12b/cc-pVTZ-F12 energies. The accuracy of the PES is confirmed by the excellent agreement of its stationary-point properties and one-dimensional potential energy curves compared with the corresponding ab initio data. The reaction probabilities and integral cross sections are calculated for the ground-state and several vibrationally excited-state reactions by quasi-classical trajectory simulations. Remarkable is that the maximum impact parameter b where reactivity vanishes is almost independent of collision energy ranging from 1 to 40 kcal mol-1, and the reaction probability increases with increasing collision energy for this negative-barrier reaction. At the same time, a slight mode-specificity effect is observed. In addition, the deuterium effect is investigated and the sudden vector projection is discussed.

ManyHF-based full-dimensional potential energy surface development and quasi-classical dynamics for the Cl + CH3NH2 reaction.

A full-dimensional spin-orbit (SO)-corrected potential energy surface (PES) is developed for the Cl + CH3NH2 multi-channel system. Using the new PES, a comprehensive reaction dynamics investigation is performed for the most reactive hydrogen-abstraction reactions forming HCl + CH2NH2/CH3NH. Hartree-Fock (HF) convergence problems in the reactant region are handled by the ManyHF method, which finds the lowest-energy HF solution considering several different initial guess orbitals. The PES development is carried out with the Robosurfer program package, which iteratively improves the surface. Energy points are computed at the ManyHF-UCCSD(T)-F12a/cc-pVDZ-F12 level of theory combined with basis set (ManyHF-RMP2-F12/cc-pVTZ-F12 - ManyHF-RMP2-F12/cc-pVDZ-F12) and SO (MRCI+Q/aug-cc-pwCVDZ) corrections. Quasi-classical trajectory simulations show that the CH3-side hydrogen abstraction occurs more frequently in contrast to the NH2-side reaction. In both cases, the integral cross sections decrease with increasing collision energy (Ecoll). A reaction mechanism shifting from indirect to direct stripping can be observed from the opacity functions, scattering angle, and translation energy distributions as Ecoll increases. Initial attack angle distributions reveal that chlorine prefers to abstract hydrogen from the approached functional group. The collision-energy dependence of the product energy distributions shows that the initial translational energy mainly transfers to product recoil. The HCl vibrational and rotational energy values are comparable and nearly independent of collision energy, while the CH2NH2 and CH3NH co-products' vibrational energy values are higher than the rotational energy values with more significant Ecoll dependence. The HCl(v = 0) rotational distributions are compared with experiment, setting the direction for future investigations.

Alternating Stereospecificity upon Central-Atom Change: Dynamics of the F- +PH2 Cl SN 2 Reaction Compared to its C- and N-Centered Analogues.

Central-atom effects on bimolecular nucleophilic substitution (SN 2) reactions are well-known in chemistry, however, the atomic-level SN 2 dynamics at phosphorous (P) centers has never been studied. We investigate the dynamics of the F- +PH2 Cl reaction with the quasi-classical trajectory method on a novel full-dimensional analytical potential energy surface fitted on high-level ab initio data. Our computations reveal intermediate dynamics compared to the F- +CH3 Cl and the F- +NH2 Cl SN 2 reactions: phosphorus as central atom leads to a more indirect SN 2 reaction with extensive complex-formation with respect to the carbon-centered one, however, the title reaction is more direct than its N-centered pair. Stereospecificity, characteristic at C-center, does not appear here either, due to the submerged front-side-attack retention path and the repeated entrance-channel inversional motion, whereas the multi-inversion mechanism discovered at nitrogen center is also undermined by the deep Walden-well. At low collision energies, 6 % of the PH2 F products form with retained configuration, mostly through complex-mediated mechanisms, while this ratio reaches 24 % at the highest energy due to the increasing dominance of the direct front-side mechanism and the smaller chance for hitting the deep Walden-inversion minimum. Our results suggest pronounced central-atom effects in SN 2 reactions, which can fundamentally change their (stereo)dynamics.

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.

The influence of fluorination on the dynamics of the F- + CH3CH2I reaction.

The competition between the bimolecular nucleophilic substitution (SN2) and base-induced elimination (E2) reaction and their intrinsic reactivity is of key interest in organic chemistry. To investigate the effect of suppressing the E2 pathway on SN2 reactivity, we compared the reactions F- + CH3CH2I and F- + CF3CH2I. Differential cross-sections have been measured in a crossed-beam setup combined with velocity map imaging, giving insight into the underlying mechanisms of the individual pathways. Additionally, we employed a selected-ion flow tube to obtain reaction rates and high-level ab initio computations to characterize the different reaction pathways and product channels. The fluorination of the ß-carbon not only suppresses the E2-reaction but opens up additional channels involving the abstraction of fluorine. The overall SN2 reactivity is reduced compared to the non-fluorinated iodoethane. This reduction is presumably due to the competition with the highly reactive channels forming FHF- and CF2CI-.

Competition between the H-abstraction and the X-abstraction pathways in the HX (X = Br, I) + C2H5 reactions.

The recently-developed high-level full-dimensional spin-orbit-corrected potential energy surfaces based on ManyHF-UCCSD(T)-F12a/cc-pVDZ-F12 + SOcorr(MRCI-F12+Q(5,3)/cc-pVDZ-F12) (cc-pVDZ-PP-F12 for the Br and I atoms) energy points for the reactions of HX (X = Br, I) with C2H5 are improved by adding three to four thousand new geometries with higher energies at the same ab initio level to cover a higher-energy range. Quasi-classical trajectory simulations in the 30-80 kcal mol-1 collision energy range on the new surfaces are performed and show that as collision energy increases, the reaction probability of the submerged-barrier H-abstraction reaction pathway decreases a bit but the reactivity of the X-abstraction reaction, which has an apparent barrier, increases significantly, which leads to the co-domination of the two reaction pathways at high collision energies. The excitation in HX vibrational mode helps both reaction pathways, but more for X-abstraction. The mode-specific excitations in C2H5 inhibit the H-abstraction, especially for CH2 wagging mode, but almost no effect is found for X-abstraction. The deuterium effect is similar for both pathways. The sudden vector projection model can only predict the HX-stretching vibrational enhancements in X-abstraction. Forward/backward scattering is favored for H/X-abstraction, indicating the dominance of the direct stripping/rebound mechanism. The decrease of reactivity for the H-abstraction reaction pathway partly comes from the fact that the H-abstraction is much pickier about the initial attack angle. The reactivity of both reaction pathways increases when side-on CH3CH2 attack happens. The major part of the initial translational energy is preserved as translational energy in the products in H-abstraction, while for X-abstraction a large amount of it is transferred into the internal energy of C2H5X.

Exploring the versatile reactivity of the F- + SiH3Cl system on a full-dimensional coupled-cluster potential energy surface.

We develop a full-dimensional analytical potential energy surface (PES) for the F- + SiH3Cl reaction using Robosurfer for automatically sampling the configuration space, the robust [CCSD-F12b + BCCD(T) - BCCD]/aug-cc-pVTZ composite level of theory for computing the energy points, and the permutationally invariant polynomial method for fitting. Evolution of the fitting error and the percentage of the unphysical trajectories are monitored as a function of the iteration steps/number of energy points and polynomial order. Quasi-classical trajectory simulations on the new PES reveal rich dynamics resulting in high-probability SN2 (SiH3F + Cl-) and proton-transfer (SiH2Cl- + HF) products as well as several lower-probability channels, such as SiH2F- + HCl, SiH2FCl + H-, SiH2 + FHCl-, SiHFCl- + H2, SiHF + H2 + Cl-, and SiH2 + HF + Cl-. The Walden-inversion and front-side-attack-retention SN2 pathways are found to be competitive, producing nearly racemic products at high collision energies. The detailed atomic-level mechanisms of the various reaction pathways and channels as well as the accuracy of the analytical PES are analyzed along representative trajectories.