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Among all the molecular species found in the interstellar medium, molecules with threefold symmetry axes play a special role, as their rotational spectroscopy allows them to act as practical gas thermometers. Methyl-cyanide (CH3CN) is the second most abundant of those (after ammonia). We compute in this paper the collisional dynamics of methyl-cyanide in collision with helium, for both the A- and the E-symmetries of CH3CN. The potential energy surface is determined using the CCSD(T)-F12b formalism and fit with convenient analytic functions. We compute the rotationally inelastic cross sections for all levels up to 510 cm−1 of collision energy, employing at low energy exact Coupled Channels methods, and at higher energies, approximate Coupled States methods. For temperatures from 7 K up to 300 K, rates of quenching are computed and most are found to differ from those reported earlier (up to a factor of a thousand), calling for a possible reexamination of the temperatures assigned to low density gasses. [ABSTRACT FROM AUTHOR]

The scattering of atomic nitrogen over a N-pre-adsorbed W(100) surface is theoretically described in the case of normal incidence off a single adsorbate. Dynamical reaction mechanisms, in particular Eley-Rideal (ER) abstraction, are scrutinized in the 0.1-3.0 eV collision energy range and the influence of temperature on reactivity is considered between 300 and 1500 K. Dynamics simulations suggest that, though non-activated reaction pathways exist, the abstraction process exhibits a significant collision energy threshold (0.5 eV). Such a feature, which has not been reported so far in the literature, is the consequence of a repulsive interaction between the impinging and the pre-adsorbed nitrogens along with a strong attraction towards the tungsten atoms. Above threshold, the cross section for ER reaction is found one order of magnitude lower than the one for hot-atoms formation. The abstraction process involves the collision of the impinging atom with the surface prior to reaction but temperature effects, when modeled via a generalized Langevin oscillator model, do not affect significantly reactivity. [ABSTRACT FROM AUTHOR]

Quasiclassical trajectories simulations are performed to study the recombiantion of Nitrogen molecules over W(110) surface. The efficiency of Eley-Rideal (ER) recombination reaction is compared with that reported on reference [Quintas et al. Rev. Cub. Fis. 27, 244 (2010)], where the ER reaction is analyzed over W(100) surface. As it has been already observed in other systems, ER reactivity increases as the interaction among the initially adsorbed atom and the substrate decreases. Over W(110) surface ER recombination probability is greater than the observed over W(100), specially at low collision energies. [ABSTRACT FROM AUTHOR]

Using the classical trajectory method, the dynamics of molecular recombination of Nitrogen atoms from a Tungsten (100) surface is studied. We focus our attention on the Eley-Rideal (ER) recombination mechanism. The potential energy surface is an extended version of the periodic London-Eyring-Polanyi-Sato potential, recently developed. The dynamics is explored in a wide range of projectile energies, the main objective being to compare the behavior of the probability for ER recombination and hot-atoms (HA) formation. [ABSTRACT FROM AUTHOR]

An updated version of the CO + CO potential energy surface from [R. Dawes, X. G. Wang and T. Carrington, J. Phys. Chem. A 2013, 117 , 7612] is presented, that incorporates an improved treatment of the asymptotic behavior. It is found that this new surface is only slightly different from the other popular PES available for this system in the literature [G. W. M. Vissers, P. E. S. Wormer and A. Van Der Avoird, Phys. Chem. Chem. Phys. 2003, 5 , 4767]. The differences are quantified by expanding both surfaces over a set of analytic functions and comparing the behavior of expansion coefficients along the molecule-molecule distance R . It is shown that all expansion coefficients behave similarly, except in the very high energy range at small R where the PES is repulsive. That difference has no effect on low collision-energy dynamics, which is explored via inelastic scattering calculations carried out using the MQCT program which implements the mixed quantum/classical theory for molecular energy exchange processes. The validity of MQCT predictions of state-to-state transition cross sections for CO + CO is also tested by comparison against full-quantum coupled-states calculations. In all cases MQCT gives reliable results, except at very low collision energy where the full-quantum calculations predict strong oscillations of state-to-state transition cross sections due to resonances. For strong transitions with large cross sections, the results of MQCT are reliable, especially at higher collision energy. For weaker transitions, and lower collision energies, the cross sections predicted by MQCT may be up to a factor of 2-3 different from those obtained by full-quantum calculations.

Water and hydrogen cyanide are two of the most common species in space and the atmosphere with the ability of binding to form dimers such as H 2 O-HCN. In the literature, while calculations characterizing various properties of the H 2 O-HCN cluster (equilibrium distance, vibrational frequencies and rotational constants) have been done in the past, extensive calculations of the rovibrational states of this system using a reliable quantum dynamical approach have yet to be reported. In this work, we intend to mend that by performing the first calculation of the rovibrational states of the H 2 O-HCN van der Waals complex on a recently developed potential energy surface. We use the block improved relaxation procedure implemented in the Heidelberg MultiConfiguration Time-Dependent Hartree (MCTDH) package to compute the states of the H 2 O-HCN isomer, from which we extract the transition frequencies and rotational constants of the complex. We further adapt an approach first suggested by Wang and Carrington-and supported here by analysis routines of the Heidelberg MCTDH package-to properly characterize the computed rovibrational states. The subsequent assignment of rovibrational states was done by theoretical analysis and visual inspection of the wavefunctions. Our simulations provide a Zero Point Energy (ZPE) and intermolecular vibrational frequencies in good agreement with past ab initio calculations. The transition frequencies and rotational constants obtained from our simulations match well with the available experimental data. This work has the broad aim to propose the MCTDH approach as a reliable option to compute and characterize rovibrational states of van der Waals complexes such as the current one.

The remote sensing of abundance and properties of HCl-the main atmospheric reservoir of Cl atoms that directly participate in ozone depletion-is important for monitoring the partitioning of chlorine between "ozone-depleting" and "reservoir" species. Such remote studies require knowledge of the shapes of molecular resonances of HCl, which are perturbed by collisions with the molecules of the surrounding air. In this work, we report the first fully quantum calculations of collisional perturbations of the shape of a pure rotational line in H35Cl perturbed by an air-relevant molecule [as the first model system we choose the R(0) line in HCl perturbed by O2]. The calculations are performed on our new highly accurate HCl(X1Σ+)-O2(X3Σg-) potential energy surface. In addition to pressure broadening and shift, we also determine their speed dependencies and the complex Dicke parameter. This gives important input to the community discussion on the physical meaning of the complex Dicke parameter and its relevance for atmospheric spectra (previously, the complex Dicke parameter for such systems was mainly determined from phenomenological fits to experimental spectra and the physical meaning of its value in that context is questionable). We also calculate the temperature dependence of the line shape parameters and obtain agreement with the available experimental data. We estimate the total combined uncertainties of our calculations at 2% relative root-mean-square error in the simulated line shape at 296 K. This result constitutes an important step toward computational population of spectroscopic databases with accurate ab initio line shape parameters for molecular systems of terrestrial atmospheric importance., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The nitrogen dioxide (NO 2 ) radical is composed of the two most abundant elements in the atmosphere, where it can be formed in a variety of ways including combustion, detonation of energetic materials, and lightning. Relevant also to smog and ozone cycles, together these processes span a wide range of temperatures. Remarkably, high-resolution NO 2 electronic absorption spectra have only been reported in a narrow range below about 300 K. Previously, we reported [ J. Phys. Chem. A 2021, 125, 5519-5533] the construction of quasi-diabatic potential energy surfaces (PESs) for the lowest four electronic states (X̃, Ã, B̃, and C̃) of NO 2 . In addition to three-dimensional PESs based on explicitly correlated MRCI(Q)-F12/VTZ-F12 ab initio data, the geometry dependence of each component of the dipoles and transition dipoles was also mapped into fitted surfaces. The multiconfigurational time-dependent Hartree (MCTDH) method was then used to compute the 0 K electronic absorption spectrum (from the ground rovibrational initial state) employing those energy and transition dipole surfaces. Here, in an extension of that work, we report an investigation into the effects of elevated temperature on the spectrum, considering the effects of the population of rotationally and vibrationally excited initial states. The calculations are complemented by new experimental measurements. Spectral contributions from hundreds of rotational states up to N = 20 and from 200 individually-characterized vibrational states were computed. A spectral simulation tool was developed that enables modeling the spectrum at various temperatures─by weighting individual spectral contributions via the partition function, or for pure excited initial states, which can be probed via transient absorption spectroscopy. We validate these results against experimental absorption spectroscopy data at high temperatures, as well as via a new measurement from the (1,0,1) initial vibrational state.

Interstellar anions play an important role in astrochemistry as being tracers of the physical and chemical conditions in cold molecular clouds and circumstellar gas. The local thermodynamic equilibrium is generally not fulfilled in media where anions are detected and radiative and collisional data are required to model the observed lines. The C2H- anion has not yet been detected in the interstellar medium; however, collisional data could be used for non-LTE models that would help in identifying the most intense lines. For this purpose, we have computed the first 4D potential energy surface (PES) of the C2H--H2 complex using an explicitly correlated coupled-cluster approach. The PES is characterized by a single deep minimum with a well-depth of 924.96 cm-1. From this interaction potential, we derived excitation cross sections and rate coefficients of C2H- induced by collisions with para- and ortho-H2. The results obtained for collisions with para-H2 are compared to previous calculations performed using a 2D-PES obtained from an average over H2 rotations., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

A four-dimensional-potential energy surface (4D-PES) of the atmospherically relevant carbon dioxide-oxygen molecule (CO 2 -O 2 ) van der Waals complex is mapped using the ab initio explicitly correlated coupled cluster method with single, double, and perturbative triple excitations (UCCSD(T)-F12b), and extrapolation to the complete basis set (CBS) limit using the cc-pVTZ-F12/cc-pVQZ-F12 bases and the l -3 formula. An analytic representation of the 4D-PES was fitted using the method of interpolating moving least squares (IMLS). These calculations predict that the most stable configuration of CO 2 -O 2 complex corresponds to a planar slipped-parallel structure with a binding energy of V ∼ -243 cm -1 . Another isomer is found on the PES, corresponding to a non-planar cross-shaped structure, with V ∼ -218 cm -1 . The transition structure connecting the two minima is found at V ∼ -211 cm -1 . We also performed comparisons with some CO 2 -X van der Waals complexes. Moreover, we provide a SAPT analysis of this molecular system. Then, we discuss the complexation induced shifts of CO 2 and O 2 . Afterwards, this new 4D-PES is employed to compute the second virial coefficient including temperature dependence. A comparison between quantities obtained in our calculations and those from experiments found close agreement attesting to the high quality of the PES and to the importance of considering a full description of the anisotropic potential for the derivation of thermophysical properties of CO 2 -O 2 mixtures.

We present ab initio calculations of the collisional broadening of the R(0) pure rotational line in CO (at 115 GHz) perturbed by O 2 . Our calculations are done in a fully quantum way by solving close-coupling quantum-scattering equations without any approximations. We also report a new, highly accurate CO-O 2 potential energy surface on which we did the quantum-scattering calculations. The calculated collisional broadening agrees with the available experimental data in a wide temperature range. The calculated collisional shift is negligible compared to the broadening, which is also consistent with the experimental data. We combine this result with our previous calculations for the same line in CO perturbed by N 2 [Jóźwiak et al., J. Chem. Phys. 154, 054314 (2021)]; the obtained air-perturbed broadening of the R(0) pure rotational line in CO and its temperature dependence perfectly agree with the HITRAN database. This result constitutes an important step toward developing a methodology for providing accurate ab initio reference data on spectroscopic collisional line-shape parameters for molecular systems relevant to the Earth's atmosphere and for populating spectroscopic line-by-line databases.

A proper description of the collisional perturbation of the shapes of molecular resonances is important for remote spectroscopic studies of the terrestrial atmosphere. Of particular relevance are the collisions between the O 2 and N 2 molecules-the two most abundant atmospheric species. In this work, we report a new highly accurate O 2 (X 3 Σ g - )-N 2 (X 1 Σ g + ) potential energy surface and use it for performing the first quantum scattering calculations addressing line shapes for this system. We use it to model the shape of the 118 GHz fine structure line in O 2 perturbed by collisions with N 2 molecules, a benchmark system for testing our methodology in the case of an active molecule in a spin triplet state. The calculated collisional broadening of the line agrees well with the available experimental data over a wide temperature range relevant for the terrestrial atmosphere. This work constitutes a step toward populating the spectroscopic databases with ab initio line shape parameters for atmospherically relevant systems.

Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth's atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner-Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. Three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four (X̃, Ã, B̃, and C̃) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground X̃ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm -1 above the zero-point energy) have a root-mean-squared error of 16.5 cm -1 . In addition, dipole moments for each of the lowest four electronic states-and the transition dipoles between them-were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ∼1.5% with no empirical adjustments.

The Born-Oppenheimer potential energy surface (PES) has come a long way since its introduction in the 1920s, both conceptually and in predictive power for practical applications. Nevertheless, nearly 100 years later-despite astonishing advances in computational power-the state-of-the-art first-principles prediction of observables related to spectroscopy and scattering dynamics is surprisingly limited. For example, the water dimer, (H 2 O) 2 , with only six nuclei and 20 electrons, still presents a formidable challenge for full-dimensional variational calculations of bound states and is considered out of reach for rigorous scattering calculations. The extremely poor scaling of the most rigorous quantum methods is fundamental; however, recent progress in development of approximate methodologies has opened the door to fairly routine high-quality predictions, unthinkable 20 years ago. In this review, in relation to the workflow of spectroscopy and/or scattering studies, we summarize progress and challenges in the component areas of electronic structure calculations, PES fitting, and quantum dynamical calculations.

The two species considered here, O2 (oxygen molecule) and Ar (argon-atom), are both abundant components of Earth's atmosphere and hence familiar collision partners in this medium. O2 is quite reactive and extensively involved in atmospheric chemistry, including Chapman's cycle of the formation and destruction of ozone; while Ar, like N2, typically plays the nevertheless crucial role of inert collider. Inert species can provide stabilization to metastable encounter-complexes through the energy transfer associated with inelastic collisions. The interplay of collision frequency and energy transfer efficiency, with state lifetimes and species concentrations, contributes to the rich and varied chemistry and dynamics found in diverse environments ranging from planetary atmospheres to the interstellar and circumstellar media. The nature and density of bound and resonance states, coupled electronic states, symmetry, and nuclear spin-statistics can all play a role. Here, we systematically investigate some of those factors by looking at the O2-Ar system, comparing rigorous quantum-scattering calculations for the 16O16O-40Ar, 18O16O-40Ar, and 18O18O-40Ar isotope combinations. A new accurate potential energy surface was constructed for this purpose holding the O2 bond distance at its vibrationally averaged distance.

Rotational excitation of interstellar PN molecules induced by collisions with H 2 is investigated. We present the first ab initio four-dimensional potential energy surface (PES) for the PN-H 2 van der Waals system. The PES was obtained using an explicitly correlated coupled cluster approach with single, double, and perturbative triple excitations [CCSD(T)-F12b]. The method of interpolating moving least squares was used to construct an analytical PES from these data. The equilibrium structure of the complex was found to be linear, with H 2 aligned at the N end of the PN molecule, at an intermolecular separation of 4.2 Å. The corresponding well-depth is 224.3 cm -1 . The dissociation energies were found to be 40.19 cm -1 and 75.05 cm -1 for complexes of PN with ortho-H 2 and para-H 2 , respectively. Integral cross sections for rotational excitation in PN-H 2 collisions were calculated using the new PES and were found to be strongly dependent on the rotational level of the H 2 molecule. These new collisional data will be crucial to improve the estimation of PN abundance in the interstellar medium from observational spectra.

The CO2-N2 complex is formed from two key components of Earth's atmosphere, and as such, has received some attention from both experimental and theoretical studies. On the theory side, a potential energy surface (PES) based on high level ab initio data was reported [Nasri et al., J. Chem. Phys., 2015, 142, 174301] and then used in more recently reported rovibrational calculations [Lara-Moreno et al., Phys. Chem. Chem. Phys., 2019, 21, 3550]. Accuracy of about 1 percent was achieved for calculated rotational transitions of the ground vibrational state of the complex, compared with previously reported microwave spectra. However, a very recent measurement of the geared bending mode frequency [Barclay et al., J. Chem. Phys., 2020, 153, 014303] recorded a value of 21.4 cm-1, which is wildly different from the corresponding calculated value of 45.9 cm-1. To provide some insight into this discrepancy, we have constructed a new more accurate PES, and used it to perform highly converged variational rovibrational calculations. Our new results yield a value of 21.1 cm-1 for that bending frequency, in close agreement with the experiment. We also obtain significantly improved predicted rotational transitions. Finally, we note that a very shallow well, previously reported as a distinct second isomer, is not found on our new PES, but rather a transition structure is seen in that location.

Among all the molecular species found in the interstellar medium, molecules with threefold symmetry axes play a special role, as their rotational spectroscopy allows them to act as practical gas thermometers. Methyl-cyanide (CH3CN) is the second most abundant of those (after ammonia). We compute in this paper the collisional dynamics of methyl-cyanide in collision with helium, for both the A- and the E-symmetries of CH3CN. The potential energy surface is determined using the CCSD(T)-F12b formalism and fit with convenient analytic functions. We compute the rotationally inelastic cross sections for all levels up to 510 cm-1 of collision energy, employing at low energy exact Coupled Channels methods, and at higher energies, approximate Coupled States methods. For temperatures from 7 K up to 300 K, rates of quenching are computed and most are found to differ from those reported earlier (up to a factor of a thousand), calling for a possible reexamination of the temperatures assigned to low density gasses.

Some reactions produce extremely hot nascent products which nevertheless can form sufficiently long-lived van der Waals (vdW) complexes-with atoms or molecules from a bath gas-as to be observed via microwave spectroscopy. Theoretical calculations of such unbound resonance states can be much more challenging than ordinary bound-state calculations depending on the approach employed. One encounters not just the floppy, and perhaps multiwelled potential energy surface (PES) characteristic of vdWs complexes, but in addition, one must contend with excitation of the intramolecular modes and its corresponding influence on the PES. Straightforward computation of the (resonance) rovibrational levels of interest, involves the added complication of the unbound nature of the wave function, often treated with techniques such as introducing a complex absorbing potential. Here, we have demonstrated that a simplified approach of making a series of vibrationally effective PESs for the intermolecular coordinates-one for each reaction product vibrational quantum number of interest-can produce vdW levels for the complex with spectroscopic accuracy. This requires constructing a series of appropriately weighted lower-dimensional PESs for which we use our freely available PES-fitting code AUTOSURF. The applications of this study are the Ar-CS and Ar-SiS complexes, which are isovalent to Ar-CO and Ar-SiO, the latter of which we considered in a previously reported study. Using a series of vibrationally effective PESs, rovibrational levels and predicted microwave transition frequencies for both complexes were computed variationally. A series of shifting rotational transition frequencies were also computed as a function of the diatom vibrational quantum number. The predicted transitions were used to guide and inform an experimental effort to make complementary observations. Comparisons are given for the transitions that are within the range of the spectrometer and were successfully recorded. Calculations of the rovibrational level pattern agree to within 0.2% with experimental measurements.

The Chapman cycle, proposed in 1930, describes the various steps in the ongoing formation and destruction of stratospheric ozone. A key step in the formation process is the stabilization of metastable ozone molecules through collisions with a third body, usually an inert collider such as N 2 . The "ozone isotopic anomaly" refers to the observation of larger-than-expected atmospheric concentrations for certain ozone isotopologues. Previous studies point to the formation steps as the origin of this effect. A possibly key aspect of the ozone formation dynamics is that of the relative efficiencies of the collisional cooling of different isotopologues. Although the substitution of low-abundance 18 O for 16 O in O 3 molecules corresponds to a relatively small net change in mass, related to this are some subtleties due to symmetry-breaking and a resulting more than doubling of the density of allowed states governed by nuclear-spin statistics for bosons. Recently, a highly accurate 3D potential energy surface (PES) describing O 3 -Ar interactions has been constructed and used to benchmark the low-lying rovibrational states of the complex. Here, using this new PES, we have studied the collisional energy-transfer dynamics using the MultiConfiguration Time Dependent Hartree method. A study of the rotationally inelastic scattering was performed for the parent 16 O 16 O 16 O-Ar system and compared with that of the 16 O 16 O 18 O-Ar isotopologue. The state-to-state cross-sections and rates from the 0 0,0 initial state to low lying excited states are reported. Analysis of these results yields insight into the interplay between small changes in the rotational constants of O 3 and the reduced mass of the O 3 -Ar collision system, combined with that of the symmetry-breaking and introduction of a new denser manifold of allowed states.

The CF + molecule is considered one of the key species for the study of fluorine chemistry in the interstellar medium (ISM). Its recent detection, as well as its potential use as a tracer for atomic fluorine in the ISM, has increased the interest in the study of the physical and chemical properties of this cation. Accurate determination of the CF + abundance in the ISM requires detailed modeling of its excitation from both radiation and collisions with the most dominant species, which are usually atomic and molecular hydrogen. Here, we report a new highly accurate potential energy surface (PES) describing the interaction between CF + and the H 2 molecule. Exact quantum time-independent calculations of the rotational excitation cross sections for collisions of CF + with both para - and ortho -H 2 are reported. Results obtained for collisions with para -H 2 are compared to previous calculations performed using an approximate PES averaged over H 2 rotation. Excitation data for collisions with ortho -H 2 are provided for the first time.

An accurate ab initio ground-state intermolecular potential energy surface (PES) was determined for the CO-CO 2 van der Waals dimer. The Lanczos algorithm was used to compute rovibrational energies on this PES. For both the C-in and O-in T-shaped isomers, the fundamental transition frequencies agree well with previous experimental results. We confirm that the in-plane states previously observed are geared states. In addition, we have computed and assigned many other vibrational states. The rotational constants we determine from J = 1 energy levels agree well with their experimental counterparts. Planar and out-of-plane cuts of some of the wavefunctions we compute are quite different, indicating strong coupling between the bend and torsional modes. Because the stable isomers are T-shaped, vibration along the out-of-plane coordinates is very floppy. In CO-CO 2 , when the molecule is out-of-plane, interconversion of the isomers is possible, but the barrier height is higher than the in-plane geared barrier height.

The cycle of formation and destruction of ozone is an important process in the atmosphere. A key step in the formation process is the stabilization of a metastable ozone molecule, which occurs through energy transfer: usually a highly excited ozone molecule loses the excess energy through inelastic collisions with a third body (M). However, the details of this energy transfer mechanism are still not well known and one of the reasons has been the lack of an accurate potential energy surface (PES). In theoretical studies, Ar is often selected as the third body when considering O3-M dynamics. However, electronic structure calculations have not previously been reported for the complex. In this paper we benchmark the electronic structure for this system, and present our first steps towards constructing a fully flexible 6D PES by obtaining a 3D PES in the rigid rotor approximation. For this purpose, to benchmark the non-bonded interactions, we performed ab initio electronic structure calculations using explicitly-correlated coupled-cluster theory extended to the complete basis set limit (CCSD(T)-F12b/CBS). A multireference-based protocol suitable to describe the 6D flexible system was developed using the explicitly-correlated multi-reference configuration interaction (MRCI-F12) method. Subsequently, we used the AUTOSURF code to construct 3D PESs for each of the two methods with global root-mean-squared errors of less than 1 cm-1. The PES is characterized by two equivalent wells on either face of the ozone molecule consistent with the symmetry of the system. Calculations of the rovibrational levels for the complex using the Multiconfigurational Time Dependent Hartree (MCTDH) method provide insight into the states and dynamics of the system. Based on symmetry analysis, the allowed states and transitions were obtained: the transition frequencies and calculated rotational constants were then compared with previously reported experimental measurements. The isotopic effect was also studied using the 16O18O16O and 16O16O18O isotopologues. Roughly a doubling in the density of allowed states is observed when the symmetry of the ozone molecule is broken.

The potential energy surface (PES) of a molecular system constitutes a cornerstone for nearly every theoretical study of spectroscopy and dynamics. We present here AUTOSURF, our freely distributed code for the automated construction of PESs. This first release treats van der Waals systems composed of two rigid fragments. A version for reactive systems with up to five atoms is under development. The AUTOSURF suite is designed to completely automate all of the steps and procedures that go into fitting various classes of PESs and facilitates certain PES refinements aimed toward specific applications in spectroscopy and dynamics. The algorithms are based on a local interpolating moving least-squares methodology and have many advanced features such as iterative refinement and symmetry recognition. The code interfaces to popular electronic structure codes such as MOLPRO and GAUSSIAN to automatically generate ab initio PESs and is well-suited for treating highly anisotropic interactions which are challenging for traditional quadrature type expansions. The niche of these algorithms is to obtain an interpolative representation of high-level electronic energies with negligible (arbitrarily small) fitting error, requiring minimal human supervision in the entire process of selection, computation, and fitting of the ab initio data. The code is designed to run in parallel on Linux-based machines ranging from small workstations to large high-performance computing clusters.

A new high quality potential energy surface is calculated at a coupled-cluster single double triple level with an aug-cc-pV5Z basis set for the HCS(+)-He system. This potential energy surface is used in low energy quantum scattering calculations to provide a set of (de)-excitation cross sections and rate coefficients among the first 20 rotational levels of HCS(+) by He in the range of temperature from 5 K to 100 K. The paper discusses the impact of the new ab initio potential energy surface on the cross sections at low energy and provides a comparison with the HCO(+)-He system. The HCS(+)-He rate coefficients for the strongest transitions differ by factors of up to 2.5 from previous rate coefficients; thus, analysis of astrophysical spectra should be reconsidered with the new rate coefficients.