Adiabatic Potential Energy Surfaces Research Articles

Quasi-Diabatization Based on Minimizing Derivative Couplings in a Limited Configuration Space: Elimination of Boundary Condition Dependence.

Due to the cuspidal ridges of adiabatic potential energy surfaces (PESs) and singularities of nonadiabatic couplings (NACs), obtaining an analytical expression for the adiabatic Hamiltonian is difficult. Thereby, nonadiabatic dynamics simulations are often carried out on-the-fly, which is time-consuming. This motivates us to construct quasi-diabatic representations, which have smooth PESs and diabatic couplings. In this study, we propose a new quasi-diabatization method based on minimizing derivative couplings (MDC) in a limited configuration space. The boundary conditions are first considered and finally released to obtain the adiabatic-to-diabatic rotation angles and transformation matrices. As demonstrated in representative one- and two-dimensional models and the widely studied linear H3 molecule, MDC performs significantly better than the direct integration quasi-diabatization approach. In particular, accurate diabatic potential energy matrices have been successfully obtained even when the NACs of all configurations in the considered space are nonnegligible.

Emergence of the Molecular Geometric Phase from Exact Electron-Nuclear Dynamics.

Geometric phases play a crucial role in diverse fields. In molecules, they appear when a reaction path encircles an intersection between adiabatic potential energy surfaces and the molecular wave function experiences quantum-mechanical interference effects. This intriguing effect, closely resembling the magnetic Aharonov-Bohm effect, crucially relies on the adiabatic description of the dynamics, and it is an open issue whether and how it persists in an exact quantum dynamical framework. Recent works suggest that the molecular geometric phase is an artifact of the adiabatic approximation, thereby challenging the entire concept. Here, building upon a recent investigation (Martinazzo, R.; Burghardt, I. Phys. Rev. Lett. 2024, 132, 243002), we address this issue using the exact factorization of the total wave function. We introduce instantaneous gauge-invariant phases separately for the electrons and nuclei and use them to monitor the phase difference between the trailing edges of a wavepacket encircling a conical intersection between adiabatic surfaces. The transition from the time-dependent open-path phase differences to the closed-path limit is examined, revealing how the phase differences in the electronic and nuclear subspaces compensate for each other upon path closure. In this way, we unambiguously demonstrate the role of the geometric phase in the interference process and shed light on its persistence beyond the adiabatic approximation.

Ortho-Para Conversion for H+ + H2 Collision in Low Temperature: A Fully Close-Coupled Time-Dependent Wave Packet Study.

The collision-induced rate coefficients of ortho-para conversion for the H+ + H2 reaction provide accurate information to probe the lifetime of cold environments in interstellar media. Rotationally resolved reaction probabilities are calculated at the low collision energy regime (0 < Ecol ≤ 0.3 eV) by employing the coupled three-dimensional (3D) time-dependent wave packet (TDWP) formalism in hyperspherical coordinates on a recently constructed ab initio ground adiabatic potential energy surface of H3+ [J. Chem. Phys. 2014, 141, 204306] for the process H+ + H2 (v = 0, j = 0-5) → H+ + H2 (v' = 0, j'). Cross-sections are then computed from the converged reaction probabilities as a function of total angular momentum (J) over the same energy regime and subsequently employed to obtain the rate constants for the ortho-to-para (O-P) and para-to-ortho (P-O) conversions and their ratio. The ratio of ortho-para conversion shows (a) appropriate convergence with the inclusion of a higher number of initial rotational states as well as a reasonable agreement with the results from a quantum statistical method and (b) a peak at lower temperature that could be due to the available collision energy for transitions involving lower rotational states (j = 0 → j' = 1).

Diabatic Potential Energy Surfaces of SrH2+ and Dynamics Studies of the Sr+(5s2S) + H2 Reaction.

Based on the ab initio energy points of both ground and excited states, a neural network fitting method combined with a specific function was successfully used to construct the diabatic potential energy surfaces (PESs) of the SrH2+ system. The topographical features of the diabatic PESs were examined in detail. The results indicate that the nonadiabatic transition characteristics between ground and excited states are accurately described by the newly constructed diabatic PESs. To verify the validity and applicability of the diabatic PESs, as well as the nonadiabatic effects during the reaction process, the quantum dynamics studies of the Sr+(5s2S) + H2 reaction were performed based on both adiabatic and diabatic PESs. The dynamics results indicate that adiabatic dynamics results are dozens of times larger than those of nonadiabatic. This illustrates the significant effect of nonadiabaticity, indicating that adiabatic dynamics results often overestimate the actual values. The integral cross sections (ICSs) were calculated and compared with the experimental data. The diabatic ICSs are in good agreement with the experimental results. The reasonable dynamics results indicate that the newly constructed diabatic PESs are suitable for the relevant dynamics studies.

Fitting of Coupled Potential Energy Surfaces via Discovery of Companion Matrices by Machine Intelligence.

Fitting coupled potential energy surfaces is a critical step in simulating electronically nonadiabatic chemical reactions and energy transfer processes. Analytic representation of coupled potential energy surfaces enables one to perform detailed dynamics calculations. Traditionally, fitting is performed in a diabatic representation to avoid fitting the cuspidal ridges of coupled adiabatic potential energy surfaces at conical intersection seams. In this work, we provide an alternative approach by carrying out fitting in the adiabatic representation using a modified version of the Frobenius companion matrices, whose usage was first proposed by Opalka and Domcke. Their work involved minimizing the errors in fits of the characteristic polynomial coefficients (CPCs) and diagonalizing the resulting companion matrix, whose eigenvalues are adiabatic potential energies. We show, however, that this may lead to complex eigenvalues and spurious discontinuities. To alleviate this problem, we provide a new procedure for the automatic discovery of CPCs and the diagonalization of a companion matrix by using a special neural network architecture. The method effectively allows analytic representation of global coupled adiabatic potential energy surfaces and their gradients with only adiabatic energy input and without experience-based selection of a diabatization scheme. We demonstrate that the new procedure, called the companion matrix neural network (CMNN), is successful by showing applications to LiH, H3, phenol, and thiophenol.

Examination of static fission properties of 236\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{236}$$\\end{document}U and 233\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{233}$$\\end{document}Th using Cassinian oval parametrization within the macroscopic–microscopic approach

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Significant Isotope Effects from the Nonadiabatic Couplings in the Cl(2P) + HD(v = 0, j = 0) Reaction.

The impact of non-Born-Oppenheimer couplings on the isotopic effects in the reaction of the Cl(2P) atom with the HD (v = 0, j = 0) molecule is investigated with our recently developed nonadiabatic time-independent quantum scattering methods, where the full open-shell characteristics are included in the six-state model, and also with the recently developed two-state model solving by time-independent methods, where part of the open-shell characteristic is included. The same reaction is also calculated with the simple adiabatic model using the lowest adiabatic potential energy surface. Compared with the results from different models, it is found that the reactivity of the Cl + HD → HCl + D channel is significantly overestimated in the adiabatic model. In contrast, the reactivity of the other channel agrees well with the nonadiabatic models. This is due to the van der Waals well in the reactant channel being changed a lot by including the nonadiabatic couplings. These quantum dynamics calculations suggest that sometimes the adiabatic model should be used with caution; otherwise, it may result in significant deviations for some reactions.

Surface Hopping with Reliable Wave Function by Introducing Auxiliary Wave Packets to Trajectory Branching.

It is well-known that the widely utilized fewest switches surface hopping method suffers from the severe overcoherence problem, and thus adiabatic populations calculated by wave functions are generally inferior to those based on active states. More importantly, to achieve a complete description of nonadiabatic dynamics, the density matrix is essential. In this paper, we present an auxiliary branching corrected surface hopping (A-BCSH) method that introduces auxiliary wave packets (WPs) on the adiabatic potential energy surfaces for trajectory branching. Both rapid and gradual separation of WP components on different surfaces are characterized, and thus the correct decoherence time along each trajectory is captured. As demonstrated in the three standard Tully models, A-BCSH exhibits excellent internal consistency. Namely, close adiabatic populations are obtained based on both wave functions and active states. In particular, A-BCSH successfully obtains a reliable time-dependent spatial distribution of the density matrix, which relies only on electronic wave functions. Due to its high performance, our A-BCSH method provides a new and highly promising perspective on further development of more consistent surface hopping with reliable wave function.

Coupled 3D (J ≥ 0) Time-Dependent Wave Packet Calculation for the F + H2 Reaction on Accurate Ab Initio Multi-State Diabatic Potential Energy Surfaces.

We had calculated adiabatic potential energy surfaces (PESs), nonadiabatic, and spin-orbit (SO) coupling terms among the lowest three electronic states (12A', 22A', and 12A″) of the F + H2 system using the multireference configuration interaction (MRCI) level of theory, and the adiabatic-to-diabatic transformation equations were solved to formulate the diabatic Hamiltonian matrix [J. Chem. Phys. 2020, 153, 174301] for the entire region of the nuclear configuration space. The accuracy of such diabatic PESs is explored by performing scattering calculations to evaluate integral cross sections (ICSs) and rate constants. The nonadiabatic and SO effects are studied by utilizing coupled 3D time-dependent wave packet formalism with zero and nonzero total angular momentum on multiple adiabatic/diabatic surfaces calculation. We depict the convergence profiles of reaction probabilities for the reactive as well as nonreactive processes on various electronic states at different collision energies with respect to total angular momentum including all helicity quantum numbers. Finally, total ICSs are calculated as functions of collision energies for the initial rovibrational state (v = 0, j = 0) of the H2 molecule along with the temperature-dependent rate coefficient, where those quantities are compared with previous theoretical and experimental results.

Parametrically Managed Activation Functions for Improved Global Potential Energy Surfaces for Six Coupled 5A' States and Fourteen Coupled 3A' States of O + O2.

We report new potential energy surfaces for six coupled 5A' states and 14 coupled 3A' states of O3. The new surfaces are created by parametrically managed diabatization by deep neural network (PM-DDNN). The PM-DDNN method uses calculated adiabatic potential energy surfaces to discover and fit an underlying adiabatic-equivalent set of diabatic surfaces and their couplings and obtains the fit to the adiabatic surfaces by diagonalization of the diabatic potential energy matrix (DPEM). The procedure yields the adiabatic surfaces and their gradients, as well as the DPEM and its gradient. If desired one can also compute the nonadiabatic coupling due to the transformation. The present work improves on previous work by using a new coordinate to guide the decay of the neural network contribution to the many-body fit to the whole DPEM. The main objective was to obtain smoother potentials than the previous ones with better suitability for dynamics calculations, and this was achieved. Furthermore, we obtained suitably small deviations from the input reference data. For the six coupled 5A' surfaces, the 60,366 data below 10 eV are fit with a mean unsigned error (MUE) of 49 meV, and for the 14 coupled 3A' surfaces, the 76,733 data below 10 eV are fit with an MUE of 28 meV. The data below 5 eV fit even more accurately with MUEs of 37 meV (5A') and 20 meV (3A').

Quantum and statistical state-to-state studies of cold Ar + H2+ collisions.

In this work we present new state-to-state integral scattering cross sections and initial-state selected rate coefficients for the 36Ar (1S) + H2+ (X2Σg+,v = 0,j) reactive system for collision energies up to 0.1 eV (with respect to the 36Ar (1S) + H2+ (X2Σg+,v = 0,j = 0) channel). To the best of our knowledge, these cross sections are the first fully state resolved ones that were obtained by performing time-independent quantum mechanical and quantum statistical calculations. For this purpose a new full-dimensional ground state 2A' adiabatic electronic potential energy surface was calculated at the MRCI+Q/aug-cc-pVQZ level of theory, which was fitted by means of machine learning methods. We find that a statistical quantum method and a statistical adiabatic channel model reproduce quantum mechanical initial-state selected cross sections fairly well, thus suggesting that complex-forming mechanisms seem to be playing an important role in the reaction dynamics of the reaction that was studied.

Rate coefficients for the O + H2 and O + D2 reactions: how well ring polymer molecular dynamics accounts for tunelling.

We present here extensive calculations of the O(3P) + H2 and O(3P) + D2 reaction dynamics spanning the temperature range from 200 K to 2500 K. The calculations have been carried out using fully converged time-independent quantum mechanics (TI QM), quasiclassical trajectories (QCT) and ring polymer molecular dynamics (RPMD) on the two lowest lying adiabatic potential energy surfaces (PESs), 13A' and 13A'', calculated by Zanchet et al. [J. Chem. Phys., 2019, 151, 094307]. TI QM rate coefficients were determined using the cumulative reaction probability formalism on each PES including all of the total angular momenta and the Coriolis coupling and can be considered to be essentially exact within the Born-Oppenheimer approximation. The agreement between the rate coefficients calculated by using QM and RPMD is excellent for the reaction with D2 in almost the whole temperature range. For the reaction with H2, although the agreement is very good above 500 K, the deviations are significant at lower temperatures. In contrast, the QCT calculations largely underestimate the rate coefficients for the two isotopic variants due to their inability to account for tunelling. The differences found in the disagreements between RPMD and QM rate coefficients for the reactions for both the isotopologues are indicative of the ability of the RPMD method to accurately describe systems where tunelling plays a relevant role. Considering that both reactions are dominated by tunelling below 500 K, the present results show that RPMD is a very powerful tool for determining rate coefficients. The present QM rate coefficients calculated on adiabatic PESs slightly underestimate the best global fits of the experimental measurements, which we attribute to the intersystem crossing with the singlet 11A' PES.

Mutual neutralization in collisions of Li+ with CN.

The mutual neutralization reaction in collisions of Li+ with CN- is a promising candidate for rigorous multi-dimensional ab initio studies of atom-molecule charge transfer processes. The reaction is driven by the non-adiabatic interaction between the lowest two 1A' electronic states at large Li-CN distances, resulting in a large cross section for mutual neutralization. As a first step, the relevant adiabatic potential energy surfaces and non-adiabatic interaction are computed ab initio, and the process is studied quantum mechanically using the vibrational sudden approximation, where the vibrational and rotational motions of the CN molecule are assumed to be frozen during the collision.

Formation Mechanisms of Electronically Excited Nitrogen Molecules from N + N2 and N + N + N Collisions Revealed by Full-Dimensional Potential Energy Surfaces.

This work reports six new full-dimensional adiabatic potential energy surfaces (PESs) of the N3 system (four 4A″ states and two 2A″ states) at the MRCI + Q/AVQZ level of theory that correlated to N2(X1Σg+) + N(4S), N2(X1Σg+) + N(2D), N2(A3Σu+) + N(4S), N2(B3Πg) + N(4S), N2(W3Δu) + N(4S), and N(4S) + N(4S) + N(4S) channels. The neural networks with a proper account of the nuclear permutation invariant symmetry of N3 were employed to fit the PESs based on about 4000 ab initio points. The accuracy of the PESs was validated by excellent agreement on the equilibrium bond length, vertical excitation energy, and dissociation energy with experimental values. Two possible mechanisms of the formation of N2(A) were found. One is that the collision occurs between N2(X) and N(4S) in the 14A″ state, followed by a nonadiabatic transition through the conical intersection with the 24A″ PES, resulting in the formation of the N2(A) + N(4S) product. The other takes place in the collision among three N(4S) atoms in the adiabatic 24A″ state, and then, N2(A) + N(4S) is formed. This is the first systematical research of the N3 system focusing on the formation of the excited states of N2 via both adiabatic and nonadiabatic pathways.

Magnitouprugost' yan-tellerovskoy podsistemy v kristallakh tipa AIIBVI, dopirovannykh khromom

The influence of an external magnetic field on the complex elastic moduli of crystals with a sphalerite or zinc blende (ZnSe) and wurtzite (CdSe) structure lightly doped by Cr2+ ions has been investigated. Measurements have been performed in the frequency interval 26–32 MHz at 1.4 K. In II–VI crystals, bivalent chromium cations are triply orbital-degenerate in the ground state and, being in a tetrahedral environment, produce Jahn–Teller complexes. These complexes are described in terms of the T ⊗ (e + t2)-problem and exhibit the adiabatic potential energy surface with the global minima of tetragonal symmetry. It has been found that in ZnSe:Cr2+ crystals, a magnetic field directed along the [001] and [110] axes influences modulus (c11 – c12)/2 and does not influence modulus c44. In CdSe:Cr2+ crystals, however, moduli c55 and c66, which are the analogs of (c11 – c12)/2 and c44, depend on the magnetic field directed along the [101¯0101¯0] and [21¯1¯021¯1¯0] axes, respectively. The discovered anomalous behavior of the elastic moduli with magnetic field has been treated in terms of a model that takes into account the crystal field, vibronic and spin-orbital interactions, and the contribution of the Jahn–Teller subsystem to isothermal moduli determined at a constant magnetic induction. Good agreement with experimental dependences of the elastic moduli in strong magnetic fields has been obtained, and it has been shown that the nonmonotonic variation in weak magnetic fields (below 2 T) should be associated with a magnetic field dependence of the relaxation time.

Relaxation processes among adiabatic potential energy surfaces of Tl+ and Au− centers in NaCl crystals

We investigated temperature dependencies of the temporal behaviors of luminescence bands attributed to the radiative transitions from adiabatic potential energy surfaces (APESs) of 1T1g, 3T2u+3Eu, 3T1g, and 3A1u of Tl+ and Au− centers in NaCl crystals. In addition to NaCl:Au−, a luminescence band with the sharp zero-phonon luminescence line was observed in NaCl:Tl+, a strong electron-lattice interaction system. A time-resolved study revealed that this luminescence band with the zero-phonon line in NaCl:Tl + exhibited the decay time of 4.3 ms at low temperatures attributed to the radiative transition from 3A1u APES. The characteristic temperature dependences of the decay time constant and luminescence intensity of the luminescence from the 3T1g and 3A1u APESs were discussed based on a configuration coordinate scheme. The intensities and decay time constants of luminescence bands caused by radiative transitions from the 1T1g, 3T2u+3Eu, 3T1g, and 3A1u APESs changed with temperature through thermally activated nonradiative transitions among APESs. The temperature dependencies of luminescence intensities and decay time constants were analyzed using rate equations that comprise radiative and nonradiative transitions from APESs and among APESs, respectively. The activation energies of APESs were estimated from the best-fit results. The characteristics of thermally activated processes among APESs are revealed in weak and strong electron-lattice interaction systems.

ANT 2023: A program for adiabatic and nonadiabatic trajectories

ANT 2023 is a program for quasiclassical and semiclassical trajectories, both single-surface trajectories for which the Born-Oppenheimer approximation is valid and multi-surface calculations with electronic state changes, i.e., for electronically adiabatic and electronically nonadiabatic trajectories. There are several methods available for multisurface problems: surface hopping with or without time uncertainty and with or without decoherence, semiclassical Ehrenfest, self-consistent decay of mixing, and coherent switching with decay of mixing (CSDM). The potential surface for single-surface problems may be an analytic potential function supplied by the user, or one may use direct dynamics. To use the adiabatic representation (i.e., electronically adiabatic basis functions) for electronically nonadiabatic dynamics, the user may either provide the adiabatic surfaces and nonadiabatic couplings by direct dynamics, or the program may calculate them from diabatic surfaces and diabatic couplings, which are usually analytic. One can also use analytic fits to the surfaces and couplings to carry out calculations entirely in the diabatic representation. The curvature-driven approximation is available as an option for use with CSDM and trajectory surface hopping. The ANT 2023 program is especially recommended for calculations with analytic potential energy surfaces and couplings because of its high efficiency for such calculations. Program SummaryProgram Title: ANT 2023, revision BCPC Library link to program files:https://doi.org/10.17632/gr74wwckcp.1Developer's repository link: https://doi.org/10.5281/zenodo.10011563Licensing Provisions: Apache-2.0Programming language: Fortran 90Interfaces to other programs: For direct dynamics, the code has well tested interfaces to the Gaussian 09 [1], Gaussian 16 [2], MOPACmn [3], and Molpro [4] electronic structure codes. The interfaces are included, but these electronic structure programs must be obtained separately. Users may also provide their own interfaces to other electronic structure programs.[1] M. J. Frisch et al. Gaussian 09, Gaussian, Inc., Wallingford CT, 2016.[2] M. J. Frisch et al., Gaussian 16, Gaussian, Inc., Wallingford CT, 2016.[3] J. J. P. Stewart et al., MOPAC 5.022mn, University of Minnesota, Minneapolis, MN, 2015; Zenodo. https://doi.org/10.5281/zenodo.8153079[4] H.-J. Werner et al., J. Chem. Phys. 152 (2020) 144107.Nature of problem: classical, quasiclassical, or semiclassical molecular dynamics for electronically adiabatic or electronically nonadiabatic collisions and unimolecular processes of atoms, molecules, and clustersSolution method: The program integrates the classical or semiclassical equations of motion for the motion of the nuclei. ANT 2023 can use anharmonic initial-state selection for initial states of diatomics or harmonic initial-state selection for general polyatomics. The equations of motion for electronically adiabatic processes are Hamilton's equations with potential energy functions corresponding to the Born-Oppenheimer approximation. The equations of motion for electronically nonadiabatic processes (non-Born-Oppenheimer processes) include trajectory surface hopping (fewest switches with or without time uncertainty and with or without decoherence) or several possible mean-field methods, including the semiclassical Ehrenfest method (also called the time-dependent Hartree method), self-consistent decay of mixing, and coherent switching with decay of mixing. Electronically nonadiabatic processes may be treated using either the adiabatic representation or a diabatic representation, and the potential surfaces and couplings may be obtained from analytic fits in a user-supplied subroutine or by direct dynamics, which involves requesting energies, gradients, and couplings as needed from a quantum chemistry electronic structure program. In the adiabatic representation, the coupling may be nonadiabatic coupling vectors (based on gradients of electronic wave functions), time-derivative couplings (based on overlaps of electronic wave functions), or curvature-driven couplings (based on the curvatures of the adiabatic potential energy surfaces).Additional comments: The ANT 2023 program authors are Y. Shu, L. Zhang, J. Zheng, Z. H. Li, A. W. Jasper, D. A. Bonhommeau, R. Valero, R. Meana-Pañeda, S. L. Mielke, Z. Varga, and D. G. Truhlar [5]; the authors of the article [6] describing ANT 2023 are Y. Shu, L. Zhang, and D. G. Truhlar.

What is Missing in the Mean Field Description of Spatial Distribution of Population? Important Role of Auxiliary Wave Packets in Trajectory Branching.

When the traditional Ehrenfest mean field approach is employed to simulate nonadiabatic dynamics, an effective wave packet (WP) on the average potential energy surface (PES) is utilized to describe the nuclear motion. In the fully quantum picture, however, the WP components on different adiabatic PESs gradually separate in space because they evolve under different velocities and forces. Due to trajectory branching of the WP components, proper decoherence needs to be taken into account, and the spatial distribution of population cannot be described by a single effective WP. Here, we propose an auxiliary branching corrected mean field (A-BCMF) method, where trajectories of auxiliary WPs on adiabatic PESs are introduced. As benchmarked in the three standard Tully models, A-BCMF not only gives correct channel populations but also captures an accurate time-dependent spatial distribution of population. Thereby, we reveal the important role of auxiliary WPs in solving intrinsic problems of the widely used mean field description of nonadiabatic dynamics.

Formation of N(2D) from Hyperthermal Collisions between O(3P) and NO(X2Π).

Hyperthermal collisions between O(3P) and NO(X2Π) could lead to the formation of the first electronically excited atomic nitrogen (N(2D)), which plays a key role in plasma formation in shock-heated air. This process is facilitated mainly by four doublet states, and to a much lesser extent by two quartet states. In this work, we report quasi-classical trajectory studies of this reactive process using the four analytical adiabatic potential energy surfaces for the doublet states developed previously from fitting high-level ab initio data. The reactions were found to be strongly enhanced by vibrational excitation of the NO reactant, consistent with the existence of potential energy barriers in the exit channel. Despite the large endothermicity of the reaction, the rate coefficient is significant at high temperatures, suggesting a possible role of this reaction in the hyperthermal kinetics in the shock layer of a hypersonic (re)entry vehicle.

Machine Learning Representations of the Three Lowest Adiabatic Electronic Potential Energy Surfaces for the ArH2+ Reactive System.

In this work, we present Gaussian process regression machine learning representations of the three lowest coupled 2A' adiabatic electronic potential energy surfaces of the ArH2+ reactive system in full dimensionality. Additionally, the nonadiabatic coupling matrix elements were calculated. These adiabatic potentials and their nonadiabatic couplings are necessary ingredients in the theoretical investigation of the nonadiabatic reaction dynamics of the Ar + H2+ → ArH+ + H and Ar+ + H2 → ArH+ + H reactions, as well as the competing charge transfer process, Ar + H2+↔ Ar+ + H2. Accurate ab initio electronic structure calculations (ic-MRCI+Q/aug-cc-pVQZ), whereby the effect of spin-orbit coupling in Ar+ has been accounted for through the state interaction method, serve as input for the machine learning training process. The potential energy surfaces are fitted with high accuracies, with root-mean-square errors on the order of 10-7 eV for the three surfaces, which meet the requirements for chemical dynamics at low temperature. It was found that quite a large number of training points (of the order of 5000 ab initio points) are needed in order to achieve these accuracies due to the complex topography of these electronic surfaces.