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.

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.

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.

Investigating music teachers' ICT skills and technical possibilities in the field of online music education during the COVID-19 pandemic.

The effectiveness of music education depends on the personal interaction between teachers and students in the pedagogical process. The presence of the music teacher, the initial presentation of music, and the immediate correction are all essential in individual instrumental training and group-based music education [1]. In our study, we examined the ICT skills and technical possibilities which music teachers (N = 352) had at their disposal during the COVID-19 pandemic, compiled the Internet platforms they used in their teaching, and asked whether they produced their own teaching materials. By using factor analysis, we explored music teachers' attitudes towards online education and identified four factors, namely student-centred, digital virtuoso, digitally creative, and difficult-to-adapt factors. The change in the learning environment and in familiar methods presented new challenges to most surveyed music teachers, who were creative in adapting to the situation and in preparing suitable teaching materials for their students.

Benchmark ab initio potential energy surface mapping of the F + CH3NH2 reaction.

This electronic structure study reveals four exothermic and two endothermic reaction pathways of the F + CH3NH2 system: the barrierless hydrogen abstraction from the methyl/amino group (HF + CH2NH2/CH3NH), amino/methyl substitution (NH2 + CH3F and CH3 + NH2F) and hydrogen substitution from the two functional groups (H + CH2FNH2/CH3NHF). The benchmark classical and adiabatic energies are obtained using a high-accuracy composite ab initio approach, where the gold-standard explicitly-correlated coupled cluster method (CCSD(T)-F12b) is applied with the correlation-consistent polarized valence quintuple-zeta F12 basis set (cc-pV5Z-F12) and further additive energy contributions. Considering indispensable post-(T) correlation, core correlation, scalar relativistic, spin-orbit and harmonic zero-point energy corrections, the obtained global minimum of the potential energy surface is the post-reaction CH2NH2⋯HF complex in the product channel. Although each substitution pathway has a high barrier, the energies of amino-substitution and methyl-hydrogen-substitution products are below the energy of the reactants, as well as the submerged-barrier hydrogen-abstraction pathways.

Benchmark Ab Initio Characterization of the Abstraction and Substitution Pathways of the Cl + CH3CN Reaction.

We investigate the reaction pathways of the Cl + CH3CN system: hydrogen abstraction, methyl substitution, hydrogen substitution, and cyanide substitution, leading to HCl + CH2CN, ClCN/CNCl + CH3, ClCH2CN + H, and CH3Cl + CN, respectively. Hydrogen abstraction is exothermic and has a low barrier, whereas the other channels are endothermic with high barriers. The latter two can proceed via a Walden inversion or front-side attack mechanism, and the front-side attack barriers are always higher. The C-side methyl substitution has a lower barrier and also a lower endothermicity than the N-side reaction. The computations utilize an accurate composite ab initio approach and the explicitly correlated CCSD(T)-F12b method. The benchmark classical and vibrationally adiabatic energies of the stationary points are determined with the most accurate CCSD(T)-F12b/aug-cc-pVQZ energies adding further contributions of the post-(T) and core correlation, scalar relativistic effects, spin-orbit coupling, and zero-point energy corrections. These contributions are found to be non-negligible to reach subchemical accuracy.

Benchmark ab initio stationary-point characterization of the complex potential energy surface of the multi-channel Cl + CH3NH2 reaction.

We characterize the exothermic low/submerged-barrier hydrogen-abstraction (HCl + CH2NH2/CH3NH) as well as, for the first time, the endothermic high-barrier amino-substitution (CH3Cl + NH2), methyl-substitution (NH2Cl + CH3), and hydrogen-substitution (CH2ClNH2/CH3NHCl + H) pathways of the Cl + CH3NH2 reaction using an accurate composite ab initio approach. The computations reveal a CH3NH2Cl complex in the entrance channel, nine transition states corresponding to different abstractions, Walden-inversion substitution, and configuration-retaining front-side attack substitution pathways, as well as nine post-reaction complexes. The global minima of the electronic and vibrationally adiabatic potential energy surfaces correspond to the pre-reaction CH3NH2Cl and post-reaction CH2NH2HCl complexes, respectively. The benchmark composite energies of the stationary points are obtained by considering basis-set effects up to the correlation-consistent polarized valence quadruple-zeta basis augmented with diffuse functions (aug-cc-pVQZ) using the explicitly-correlated coupled-cluster singles, doubles, and perturbative triples CCSD(T)-F12b method, post-(T) correlation up to CCSDT(Q) including full triples and perturbative quadruples, core correlation, and scalar relativistic and spin-orbit effects, as well as harmonic zero-point energy corrections.