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While the growing realization of the importance of long-range interactions is being demonstrated in cold and ultracold bimolecular collision experiments, their influence on one of the most critical ion-neutral reactions has been overlooked. Here, we address the non-Langevin abrupt decrease observed earlier in the low-energy integral cross-sections and rate coefficients of the astrochemically important H + HeH + → H 2 + + He reaction. We attribute this to the presence of artificial barriers on existing potential energy surfaces (PESs). By incorporating precise long-range interaction terms, we introduce a new refined barrierless PES for the electronic ground state of HeH 2 + reactive system, aligning closely with high-level ab initio electronic energies. Our findings, supported by various classical, quantum, and statistical methods, underscore the significance of long-range terms in accurately modeling reactive PESs. The low-temperature rate coefficient on this new PES shows a substantial enhancement as compared to the previous results and aligns with the Langevin behavior. This enhancement could noticeably affect the prediction of HeH+ abundance in early Universe condition. [ABSTRACT FROM AUTHOR]

We derive the non-adiabatic ring polymer molecular dynamics (RPMD) approach in the phase space of the SU(N) Lie Group. This method, which we refer to as the spin mapping non-adiabatic RPMD (SM-NRPMD), is based on the spin-mapping formalism for the electronic degrees of freedom (DOFs) and ring polymer path-integral description for the nuclear DOFs. Using the Stratonovich–Weyl transform for the electronic DOFs and the Wigner transform for the nuclear DOFs, we derived an exact expression of the Kubo-transformed time-correlation function (TCF). We further derive the spin mapping non-adiabatic Matsubara dynamics using the Matsubara approximation that removes the high frequency nuclear normal modes in the TCF and derive the SM-NRPMD approach from the non-adiabatic Matsubara dynamics by discarding the imaginary part of the Liouvillian. The SM-NRPMD method has numerical advantages compared to the original NRPMD method based on the Meyer–Miller–Stock–Thoss (MMST) mapping formalism due to a more natural mapping using the SU(N) Lie Group that preserves the symmetry of the original system. We numerically compute the Kubo-transformed position auto-correlation function and electronic population correlation function for three-state model systems. The numerical results demonstrate the accuracy of the SM-NRPMD method, which outperforms the original MMST-based NRPMD. We envision that the SM-NRPMD method will be a powerful approach to simulate electronic non-adiabatic dynamics and nuclear quantum effects accurately. [ABSTRACT FROM AUTHOR]

This is an I easier approach to implement into computer code i , because these equations [Eq. (95) of the paper] are simpler than the corresponding EOMs for { I i SB I n i sb , I i SB I n i sb }. CLARIFICATION ON THE NUMERICAL ALGORITHM USED TO PROPAGATE DYNAMICS We want to clarify the numerical algorithm we used to propagate the EOMs and generate all numerical results presented in the paper. In the above expressions, to compute HT ht , we use Eq. (C2) of the paper. [Extracted from the article]

We present the rigorous theoretical framework of the generalized spin mapping representation for non-adiabatic dynamics. Our work is based upon a new mapping formalism recently introduced by Runeson and Richardson [J. Chem. Phys. 152, 084110 (2020)], which uses the generators of the s u (N) Lie algebra to represent N discrete electronic states, thus preserving the size of the original Hilbert space. Following this interesting idea, the Stratonovich–Weyl transform is used to map an operator in the Hilbert space to a continuous function on the SU(N) Lie group, i.e., a smooth manifold which is a phase space of continuous variables. We further use the Wigner representation to describe the nuclear degrees of freedom and derive an exact expression of the time-correlation function as well as the exact quantum Liouvillian for the non-adiabatic system. Making the linearization approximation, this exact Liouvillian is reduced to the Liouvillian of several recently proposed methods, and the performance of this linearized method is tested using non-adiabatic models. We envision that the theoretical work presented here provides a rigorous and unified framework to formally derive non-adiabatic quantum dynamics approaches with continuous variables and connects the previous methods in a clear and concise manner. [ABSTRACT FROM AUTHOR]

We report a large set of state-to-state rate constants for the H + HD reactive collision, using Quasi-Classical Trajectory (QCT) simulations on the accurate H3 global potential energy surface of Mielke et al. [J. Chem. Phys. 116, 4142 (2002)]. High relative collision energies (up to ≈56 000 K) and high rovibrational levels of HD (up to ≈50 000 K), relevant to various non thermal equilibrium astrophysical media, are considered. We have validated the accuracy of our QCT calculations with a new efficient adaptation of the Multi Configuration Time Dependent Hartree (MCTDH) method to compute the reaction probability of a specific reactive channel. Our study has revealed that the high temperature regime favors the production of H2 in its highly rovibrationnally excited states, which can de-excite radiatively (cooling the gas) or collisionally (heating the gas). Those new state-to-state QCT reaction rate constants represent a significant improvement in our understanding of the possible mechanisms leading to the destruction of HD by its collision with a H atom. [ABSTRACT FROM AUTHOR]

We report state-to-state quasi-classical trajectory rate constants for the D + H2 reactive collision, using the accurate H3 global potential energy surface of Mielke et al. [J. Chem. Phys. 116, 4142 (2002)]. High relative collision energies (up to ≈56 000 K) and high rovibrational levels of H2 (up to ≈50 000 K), relevant to various astrophysical media, are considered. The HD product molecule is formed in highly excited rovibrational states, over a wide collision energy range. The collision-induced dissociation channel (often overlooked in fully quantum reaction dynamics calculations) is found to be significantly populated, even at collision energies as low as 1500 K. [ABSTRACT FROM AUTHOR]

The reaction between D+ and H2 plays an important role in astrochemistry at low temperatures and also serves as a prototype for a simple ion–molecule reaction. Its ground X˜1A′ state has a very small thermodynamic barrier (up to 1.8 × 10−2 eV) and the reaction proceeds through the formation of an intermediate complex lying within the potential well with a depth of at least 0.2 eV, thus representing a challenge for dynamical studies. In the present work, we analyze the title reaction within the temperature range of 20–100 K by means of ring polymer molecular dynamics (RPMD) and quasi-classical trajectory (QCT) methods over the full-dimensional global potential energy surface developed by Aguado et al. [A. Aguado, O. Roncero, C. Tablero, C. Sanz and M. Paniagua, J. Chem. Phys., 2000, 112, 1240]. The computed thermal RPMD and QCT rate coefficients are found to be almost independent of temperature and fall within the range of 1.34–2.01 × 10−9 cm3 s−1. They are also in very good agreement with previous time-independent quantum mechanical and statistical quantum method calculations. Furthermore, we observe that the choice of asymptotic separation distance between the reactants can markedly alter the rate coefficient in the low temperature regime (20–50 K). Therefore it is of utmost importance to correctly assign the value of this parameter for dynamical studies, particularly at very low temperatures of astrochemical importance. We finally conclude that the experimental rate measurements for the title reaction are highly desirable in future. [ABSTRACT FROM AUTHOR]

The H + HeH + → He + H 2 + reaction has been studied by means of a combination of theoretical approaches: a statistical quantum method (SQM), ring polymer molecular dynamics (RPMD), and the quasiclassical trajectory (QCT) method. Cross sections and rate constants have been calculated in an attempt to investigate the dynamics of the process. The comparison with previous calculations and experimental results reveals that despite the fact that statistical predictions seem to reproduce some of the overall observed features, the analysis at a more detailed state-to-state level shows noticeable deviations from a complex-forming dynamics. We find some differences in cross sections and rate constants obtained in the QCT calculation with a Gaussian binning procedure with respect to previous works in which the standard histogram binning was employed.