Ab Initio Potential Energy Surface Research Articles

ExoMol line lists – LI. Molecular line lists for lithium hydroxide (LiOH)

ABSTRACT New molecular line lists for lithium hydroxide (6Li16O1H and 7Li16O1H isotopologues) covering wavelengths λ > 1 $\mu$m (0–10 000 cm−1 range) are presented. Each line list contains around 300 million transitions between rotation–vibration energy levels with total angular momentum up to J = 95, applicable for temperatures up to T ≈ 3500 K. Line list calculations were based on a previously published, high-level ab initio potential energy surface and a newly computed dipole moment surface of the ground $\tilde{X}\, ^1\Sigma ^+$ electronic state. Lithium-containing molecules are important in a variety of stellar objects and there is potential for LiOH to be observed in the atmospheres of exoplanets. Transit spectra are simulated using the rocky super-Earth 55 Cancri e as an example with two different atmospheric scenarios including LiOH. This work provides the first, comprehensive line lists of LiOH to facilitate its future molecular detection. The OYT7 line lists along with the associated temperature- and pressure-dependent molecular opacities can be downloaded from the ExoMol database at www.exomol.com and the CDS astronomical database.

Ab Initio Potential Energy Surface and Vibration-Rotation Energy Levels of Aluminum Monohydroxide.

The potential energy surface and vibration-rotation energy levels of aluminum monohydroxide in the X̃ 1A' electronic state have been determined from ab initio calculations. The equilibrium configuration of the AlOH molecule was found to be bent, although with a wide AlOH angle of 163° and a small barrier to linearity of just 4 cm-1. The AlOH molecule was definitely confirmed to be quasilinear. The predicted spectroscopic constants of the AlOH, AlOD, 26AlOH, and Al18OH isotopologues can be useful in a future analysis of high-resolution vibration-rotation spectra of these species.

Rotational energy transfer in the collision of N2O with He atom.

The quantum state-to-state rotationally inelastic quenching of N2O by colliding with a He atom is studied on an abinitio potential energy surface with N2O lying on its vibrational ground state. The cross sections for collision energies from 10-6-100cm-1 and rate constants from 10-5-10K are calculated employing the fully converged quantum close-coupling method for the quenching of the j = 1-6 rotational states of N2O. Numerous van der Waals shapes or Feshbach resonances are observed; the cross sections of different channels are found to follow the Wigner scaling law in the cold threshold regime and may intersect with each other. In order to interpret the mechanism and estimate the cross sections of the rotational energy transfer, we propose a minimal classical model of collision between an asymmetric double-shell ellipsoid and a point particle. The classical model reproduces the quantum scattering results and points out the attractive interactions and the potential asymmetry can affect the collision process. The resulting insights are expected to expand our interpretations of inelastic scattering and energy transfer in molecular collisions.

An improved artificial neural network fit of the ab initio potential energy surface points for HeH+ + H2 and its ensuing rigid rotors quantum dynamics

Artificial neural networks (ANN) have been shown for the last several years to be a versatile tool for fitting ab initio potential energy surfaces. We have demonstrated recently how a 60-neuron ANN could successfully fit a four-dimensional ab initio potential energy surface for the rigid rotor HeH+ - rigid rotor H2 system with a root-mean-squared deviation (RMSD) of 35 cm−1. We show in the present study how a (40, 40) neural network with two hidden layers could achieve a better fit with an RMSD of 5 cm−1. Through a follow-up quantum dynamical study of HeH+(j1)-H2(j2) collisions, it is shown that the two fits lead to slightly different rotational excitation and de-excitation cross sections but are comparable to each other in terms of magnitude and dependence on the relative translational energy of the collision partners. When averaged over relative translational energy, the two sets of results lead to rate coefficients that are nearly indistinguishable at higher temperatures thus demonstrating the reliability of the ANN method for fitting ab initio potential energy surfaces. On the other hand, we also find that the de-excitation rate coefficients obtained using the two different ANN fits differ significantly from each other at low temperatures. The consequences of these findings are discussed in our conclusions.

Interaction of methanol with molecular hydrogen: Ab initio potential energy surface and scattering calculations.

The potential energy surface (PES) describing the interaction of the methanol molecule with molecular hydrogen has been calculated by the use of the explicitly correlated coupled cluster method, including single, double, and (perturbative) triple excitations [CCSD(T)-F12a] and a correlation-consistent aug-cc-pVTZ basis, with the assumption of fixed molecular geometries. The computed points were fit to a functional form appropriate for time-independent quantum scattering calculations of rotationally inelastic cross sections and rate coefficients. Stationary points on the PES were located, and the global minimum was found to have an energy equal to -254.7 cm-1 relative to the energy of the separated molecules. This PES was used in time-independent close coupling quantum scattering calculations to determine state-to-state cross sections and rate coefficients for rotational transitions within the A- and E-type nuclear spin torsional ground states.

A numerical-tensorial "hybrid" nuclear motion Hamiltonian and dipole moment operator for spectra calculation of polyatomic nonrigid molecules.

The analysis and modeling of high-resolution spectra of nonrigid molecules require a specific Hamiltonian and group-theoretical formulation that differs significantly from that of more familiar rigid systems. Within the framework of Hougen-Bunker-Johns (HBJ) theory, this paper is devoted to the construction of a nonrigid Hamiltonian based on a suitable combination of numerical calculations for the nonrigid part in conjunction with the irreducible tensor operator method for the rigid part. For the first time, a variational calculation from abinitio potential energy surfaces is performed using the HBJ kinetic energy operator built from vibrational, large-amplitude motion, and rotational tensor operators expressed in terms of curvilinear and normal coordinates. Group theory for nonrigid molecules plays a central role in the characterization of the overall tunneling splittings and is discussed in the present approach. The construction of the dipole moment operator is also examined. Validation tests consisting of a careful convergence study of the energy levels as well as a comparison of results obtained from independent computer codes are given for the nonrigid molecules CH2, CH3, NH3, and H2O2. This work paves the way for the modeling of high-resolution spectra of larger nonrigid systems.

Modification of Thermal Chemical Rates in a Cavity via Resonant Effects in the Collective Regime.

The modification of thermal chemical rates in Fabry-Perot cavities, as observed in experiments, still poses theoretical challenges. While we have a better grasp of how the reactivity of isolated molecules and model systems changes under strong coupling, we lack a comprehensive understanding of the combined effects and the specific roles played by activated and spectator molecules during reactive events. In this study, we investigate an ensemble of randomly oriented gas-phase HONO molecules undergoing a cis-trans isomerization reaction on an ab initio potential energy surface. One thermally activated molecule can overcome the reaction barrier, while the other molecules are nonactivated but coupled to the cavity as well. Using the classical reactive flux method, we analyze the transmission coefficient and determine the conditions that lead to accelerated rates within the collective regime. We identify two main mechanistic aspects: First, nonactivated molecules enhance the cavity's ability to dissipate excess energy from the activated molecule postreactive event. Second, the activated molecule couples with the polaritonic resonance created by the nonactivated molecules and the cavity at a shifted resonance frequency with respect to the bare cavity.

Hyperactive learning for data-driven interatomic potentials

Data-driven interatomic potentials have emerged as a powerful tool for approximating ab initio potential energy surfaces. The most time-consuming step in creating these interatomic potentials is typically the generation of a suitable training database. To aid this process hyperactive learning (HAL), an accelerated active learning scheme, is presented as a method for rapid automated training database assembly. HAL adds a biasing term to a physically motivated sampler (e.g. molecular dynamics) driving atomic structures towards uncertainty in turn generating unseen or valuable training configurations. The proposed HAL framework is used to develop atomic cluster expansion (ACE) interatomic potentials for the AlSi10 alloy and polyethylene glycol (PEG) polymer starting from roughly a dozen initial configurations. The HAL generated ACE potentials are shown to be able to determine macroscopic properties, such as melting temperature and density, with close to experimental accuracy.

Accurate ab initio potential energy surface, rovibrational energy levels and resonance interactions of triplet ( 3 B1 ) methylene.

In this work, we report rovibrational energy levels for four isotopologues of methylene (CH2 , CHD, CD2 , and 13 CH2 ) in their ground triplet electronic state ( 3 B1 ) from variational calculation up to ~10,000 cm-1 and using a new accurate ab initio potential energy surface (PES). Triplet methylene exhibits a large-amplitude bending vibration and can reach a quasilinear configuration due to its low barrier (~2000 cm-1 ). To construct the ab initio PES, the Dunning's augmented correlation-consistent core-valence orbital basis sets were employed up to the sextuple-ζ quality [aug-cc-pCVXZ, X = T, Q, 5, and 6] combined with the single- and double-excitation unrestricted coupled cluster approach with a perturbative treatment of triple excitations [RHF-UCCSD(T)]. We have shown that the accuracy of the ab initio energies is further improved by including the corrections due to the scalar relativistic effects, DBOC and high-order electronic correlations. For the first time, all the available experimental rovibrational transitions were reproduced with errors less than 0.12 cm-1 , without any empirical corrections. Unlike more "traditional" nonlinear triatomic molecules, we have shown that even the energies of the ground vibrational state (000) with rather small rotational quantum numbers are strongly affected by the very pronounced rovibrational resonance interactions. Accordingly, the polyad structure of the vibrational levels of CH2 and CD2 was analyzed and discussed. The comparison between the energy levels obtained from the effective Watson A-reduced Hamiltonian, from the generating-function approach and from a variational calculation was given.

Ab initio potential energy surfaces for the O2-O2 system and derived thermophysical properties.

New intermolecular potential energy surfaces (PESs) for the quintet, triplet, and singlet states of two rigid oxygen (O2) molecules in their triplet ground electronic states were developed. Quintet interaction energies were obtained for 896 O2-O2 configurations by supermolecular coupled cluster (CC) calculations at levels up to CC with single, double, triple, and perturbative quadruple excitations [CCSDT(Q)] with unrestricted Hartree-Fock (UHF) reference wave functions. Corrections for scalar relativistic effects were calculated as well. Triplet interaction energies were obtained by combining the quintet interaction energies with accurate estimates for the differences between the quintet and triplet energies obtained at the UHF-CCSD(T) level of theory. Here, we exploited the fact that the triplet state is almost identical to the readily accessible "broken-symmetry" state, as shown by Valentin-Rodríguez et al. [J. Chem. Phys. 152, 184304 (2020)]. The singlet interaction energies were estimated from the quintet and triplet interaction energies by employing the Heisenberg Hamiltonian description of the spin splittings. The three PESs are represented analytically by site-site models with five sites per molecule and anisotropic site-site interactions. To validate the PESs, we calculated at temperatures from 55 to 2000K the second virial coefficient using statistical thermodynamics and the shear viscosity, thermal conductivity, and self-diffusion coefficient in the dilute gas phase using the kinetic theory of molecular gases. The calculated property values are in excellent agreement with the most accurate experimental data from the literature. Therefore, we also propose new reference correlations for the investigated properties based solely on the calculated values.

Long-range ab initio potential energy surface for the ground electronic state of the ozone molecule with the accurate dissociation asymptote

In this work an excellent agreement was achieved between the empirical (9230.08 ± 4.85 cm−1) and theoretical (9230.70 cm−1) values of the first dissociation limit (De) of O3. Ab initio multireference calculations were performed for the first time using the extended complete active space [CAS(24,15)] reference in the icMRCI(Q) method combined with the extrapolation to the complete basis set limit [CBS(56Z)] and with the inclusion of the spin–orbit coupling between 9 multiplet electronic states approaching De. Finally, the full-dimensional potential energy surface was developed in the scattering coordinates for the long-range region toward De at this level of theory.

Ab Initio Potential Energy Surfaces and Vibrational Spectra of Thioformaldehyde

Ab Initio Potential Energy Surfaces and Vibrational Spectra of Thioformaldehyde

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.

4D potential energy surface of NCCN-H2 collision: Rotational dynamics by p-H2 and o-H2 at interstellar temperatures.

The rotational excitation rates of NCCN species are studied for its collision with hydrogen (H2) in temperatures ranging from 1 to 100K. Such collisions can occur in the interstellar medium with H2 in either para (p-) or ortho (o-) state, of which the p-H2 state can be approximated via its collision with He (using a scaling factor) or with a reduced rigid rotor-H2 surface (by averaging over various orientations of H2). In the current work, a four-dimensional (4D) abinitio potential energy surface (PES) is considered to study the collision dynamics of H2 in both p- and o-states and the results are compared with previous approximations. The 4D surface is constructed using the explicitly correlated coupled-cluster method CCSD(T)-F12b with the augmented triple zeta basis AVTZ and then fitted into an artificial neural networks (NN) model to augment the surface and account for missing data points. The radial coefficients are obtained from this NN fitted 4D PES via a least square fit over two spherical harmonics functions. The cross sections (σ) are computed using the close-coupling (CC) method (until 230 cm-1) for both p- and o-H2 collisions, and the rates are obtained by Boltzmann distribution over the translational energy of H2 until 100K. The o-H2 rates are found to be higher by 25%-30% and 10%-20% compared to the p-H2 rates for Δj = 2 and higher order transitions, respectively. The coupled-state/centrifugal sudden approximated rates are also computed and found to have deviations as large as 40% when compared to CC rates, thus making quantitative descriptions unreliable.

First principles simulation of reacting hypersonic flow over a blunt wedge

This article presents molecular-level analysis of a reactive, near-continuum, Mach 21 nitrogen flow over a blunt wedge using the direct molecular simulation (DMS) method. The flow conditions lead to internal energy excitation and dissociation in the flow field, resulting in thermal and chemical nonequilibrium in the flow. Thermal nonequilibrium in the vibrational mode is observed to extend to the molecular level, where the vibrational energy distributions at various points in the flow field are observed to be non-Boltzmann. Furthermore, this is the first reactive DMS calculation where the wall is assumed to be isothermal and full momentum accommodation of the particles is enforced, hence incorporating viscous wall effects. Since the DMS method uses a quantum mechanically generated interaction potential as its only modeling input, all thermochemical and transport properties of the flow field can directly be attributed to the ab initio potential energy surface. Using the DMS solution as a benchmark, this article assesses the performance of Navier–Stokes computational fluid dynamics solutions using lower fidelity two-temperature models. Two models are chosen as points of comparison: the well-known Park two-temperature model and the recently developed modified Marrone and Treanor model.

Anharmonic Assignment of the Water Octamer Spectrum in the OH Stretch Region.

We interface the quasi-classical trajectory approach with an ab initio potential energy surface for water to assign the vibrational spectroscopical features of the OH stretch region of the water octamer cluster, which is considered to be a precursor of ice. An attempt by Li et al. to assign their recent reference experiment involved lower-level calculations based on an ad hoc scaled harmonic approach. Differently from the conclusions of this previous assignment, which invoked the contribution of 5 conformers and a solvated form of the water heptamer in the spectrum, we find out that the spectroscopic features can be related to the 4 conformers of the octamer lying lower in energy.

PO+−He collision: ab initio potential energy surface and inelastic rotational rate coefficients

ABSTRACT Computations involving quantum dynamics are performed to attain cross-sections corresponding to rotational de-excitation and excitation rates of the PO+ species including four rotational lines recently detected in the interstellar molecular clouds. New ab initio potential energy surface (PES) for PO+−He collision is constructed by using CCSD(T) method and basis set extrapolated to complete basis set limit (CBS) considering a rigid rotor approximation. The PES is then trained to create neural network (NN) model to construct an augmented surface with angular coordinates at 1° intervals. The PES has a global minimum located at $\theta =110{}^{\circ }$ and R = 3.1 Å. An analytical fitting is performed on the NN surface to obtain the first 41 radial coefficients needed to solve the equations of the coupled-channel method. The essentially precise close coupling approach is used to compute the rotational (de-)excitation cross-sections till 1400 cm−1 with rotational states converged up to 26. Further, these cross-sections are thermally averaged to get the rate coefficients for various rotational transitions till 200 K. The propensity rule favours the odd transitions (Δj = 1) for the current study. The rate for the transition 5 → 4 is found to be higher than transition 1→ 0 by a factor of 3.1 at T = 20 K that decreases to 2.1 at T = 100 K.

An approach based on genetic algorithms and machine learning coupled for studying alloy and molecular clusters by optimizing quantum energy surfaces.

A new genetic algorithm has been proposed focusing on direct ab initio potential energy surface (PES) global minima search. Besides the commonly used operators, this new approach uses an operator to: improve the initial cluster generation, classify and compare all generated clusters, and use machine learning to model the quantum PES used in parallel optimization. Part of the validation process for this methodology was done with ( for ) and ( , and 75). The results are in fair agreement with the literature and led to a new global minimum for . A search has been done for the lowest energies of nanoclusters with 2-8 atoms using the DFT approach and for , using DLPNO-CCSD(T) approach. NQGA successfully performed the MP2 optimizations for cluster. In all cases, the proposed genetic algorithm located the previously reported global minima with very efficient performance. The new proposed methodology makes it possible to optimize cluster geometries directly using high-level ab initio methods relinquishing any bias introduced by a classical approach. Our results show that this proposed method has great potential applications due to its flexibility and efficiency in identifying global minima in the tested atomic systems.

Analysis of experimental spectra of phosphine in the Tetradecad range near 2.3 μm using ab initio calculations

Due to its major interest for the chemistry of planetary atmospheres and exobiology, accurate spectroscopy data of phosphine are required for the search of signatures of this molecule in astronomical observations. In this work, high resolution infrared laboratory spectra of phosphine were analyzed for the first time in the full Tetradecad region (3769–4763 cm−1) involving 26 rotationally resolved bands. Overall, 3242 lines were assigned in spectra previously recorded by Fourier transform spectroscopy at temperatures 200 K and 296 K, using a combined theoretical model based on ab initio calculations. The total nuclear motion Hamiltonian of PH3 including ab initio potential energy surface, was reduced to an effective Hamiltonian using the high-order contact transformation method adapted to vibrational polyads of the AB3 symmetric top molecules, followed by empirical optimization of the parameters. At this step, the experimental line positions were reproduced with a standard deviation of 0.0026 cm−1 that provided unambiguous identification of observed transitions. The effective dipole transition moments of the bands were obtained by fitting to the intensities obtained from variational calculations using the ab initio dipole moment surface. The assigned lines were used to newly determine 1609 experimental vibration-rotational levels up to Jmax = 18 with energy in the range 3896–6037 cm−1 that represents significant extension towards higher energies compared to previous works. Transitions for all 26 sublevels of the Tetradecad were identified but with noticeably fewer transitions for fourfold excited bands because of their weaker intensity. At the final step, pressure-broadened half widths were attached to each transition and a composite line list adopting ab initio intensities and empirical line positions corrected to the accuracy of about 0.001 cm−1 for strong and medium transitions was validated against experimental spectra available in the literature.

Dynamics of the Cl- + CH3I reaction on a high-level abinitio analytical potential energy surface.

We have developed a full-dimensional analytical abinitio potential energy surface (PES) for the Cl- + CH3I reaction using the Robosurfer program system. The energy points have been computed using a robust composite method defined as CCSD-F12b + BCCD(T) - BCCD with the aug-cc-pVTZ(-PP) basis set and have been fitted by the permutationally invariant polynomial approach. Quasi-classical trajectory simulations on the new PES reveal that two product channels are open in the collision energy (Ecoll) range of 1-80 kcal/mol, i.e., SN2 leading to I- + CH3Cl and iodine abstraction (above ∼45 kcal/mol) resulting in ICl- + CH3. Scattering angle, initial attack angle, product translational energy, and product internal energy distributions show that the SN2 reaction is indirect at low Ecoll and becomes direct-rebound-back-side (CH3-side) attack-type, as Ecoll increases. Iodine abstraction mainly proceeds with direct stripping mechanism with side-on/back-side attack preference. Comparison with crossed-beam experiments and previous direct dynamics simulations shows quantitative or qualitative agreement and also highlights possible theoretical and/or experimental issues motivating further research.