Mixed quantum/classical calculations of rotationally inelastic scattering in the CO + CO system: a comparison with fully quantum results.

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.

MEDICAL-SURGICAL MANAGEMENT OF INTESTINAL INFECTION BY PROSTHENORCHIS ELEGANS IN NONHUMAN PRIMATES FROM COSTA RICA.

Parasitism is one of the most important diseases in nonhuman primates (NHP). Parasitism by Prosthenorchis elegans can be a threat to health and conservation of NHP in Costa Rica. Surgical management of intestinal acanthocephalan infection in two squirrel monkeys (Saimiri oerstedii) and one white-faced monkey (Cebus imitator) is described as an alternative to the lack of pharmacologic control options when there is a high burden of parasites present. A complete physical evaluation, including medical ultrasound techniques, allow for diagnosis of the parasite and its lesions. When animals present with a high burden of parasites, surgical management has shown to promote good health outcomes and increase the probability of survival.

Rovibrational states calculations of the H2O-HCN heterodimer with the multiconfiguration time dependent Hartree method.

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 H2O-HCN. In the literature, while calculations characterizing various properties of the H2O-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 H2O-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 H2O-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.

Temperature Dependence of the Electronic Absorption Spectrum of NO2.

The nitrogen dioxide (NO2) 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 NO2 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 NO2. 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.

Ab initio quantum scattering calculations and a new potential energy surface for the HCl(X1Σ+)-O2(X3Σg-) system: Collision-induced line shape parameters for O2-perturbed R(0) 0-0 line in H35Cl.

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.

Collisional excitation of C2H- by H2: New interaction potential and scattering calculations.

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.

Association between Covid-19 sources of information, beliefs, and vaccination rates: an EU-wide survey.

BACKGROUND: Misinformation hampers vaccine uptake. The European Union (EU) employed a coordinated effort to curb misinformation during the Covid-19 pandemic. In this context, we investigated relationships between sources of information, vaccine safety/effectiveness, satisfaction with government vaccination strategy, and vaccination intent. METHODS: We used cross-sectional survey data (May 2021) from Flash Eurobarometer 494, a population-adjusted dataset comprised of a representative sample of those ≥15 years from 27 EU nations. We employed a latent class analysis to create clusters of information sources as the independent variable and beliefs in vaccine safety/efficacy, satisfaction with government vaccination strategy, and vaccine intent as four outcome variables. We first estimated the association between source clusters and each of the first three outcomes separately. Then, using these three as intermediate variables, we employed structural equation modeling to estimate the relationship between sources and vaccine intent. We adjusted for individual and country-level variables. RESULTS: Among 23 012 respondents, four clusters of information sources emerged: (1) national authorities/health professionals (n = 9602; 42%), (2) mostly health professionals (6184; 27%), (3) mixed (n = 1705; 17%) and (4) social media/family/friends (n = 5524; 24%). Using cluster (3) as the referent, we found decreasing odds of beliefs in vaccine safety/effectiveness, satisfaction and vaccine intent across clusters (1), (2) and (4), respectively. Demographics played a role. CONCLUSION: In the context of the Covid pandemic, these results provide the first EU-wide estimates of the association between sources of information about vaccine safety/effectiveness, satisfaction and vaccine intent. The coordinated approach promulgated by the EU to minimize misinformation provides a model for managing future pandemics.

Urban-rural differences in perceived environmental opportunities for physical activity: a 2002-2017 time-trend analysis in Europe.

Urban-rural disparities in resources, services and facilities not only impact daily living conditions but also contribute to inequalities in physical activity, which may be associated with variations in basic public resources between urban and rural areas. This study aims to examine the evolution of perceived opportunities for physical activity in European urban and rural environments from 2002 to 2017 and their association with an active lifestyle. Data from four waves (2002, 2005, 2013 and 2017) of cross-sectional Eurobarometer surveys were collected (n = 101 373), and multilevel binomial logistic regressions were conducted. Firstly, the time trend of perceived opportunities for physical activity between urban and rural environments was explored, and secondly, the effect of urban-rural perceived opportunities on achieving an active lifestyle over the years was estimated. The findings revealed that individuals residing in rural settings encountered less opportunities to be physically active. Conversely, urban settings experienced an increase in perceived opportunities. The significance of health promotion through perceived physical activity opportunities lies in the increased likelihood of being physically active, regardless of place of residence or individual socioeconomic factors [in the area: odds ratio (OR) = 1.40, 95% confidence interval (CI) = 1.34-1.47; provided by local sport clubs: OR = 1.29, 95% CI = 1.23-1.35]. Modifying environmental aspects, such as enhancing the quantity, quality and accessibility of physical activity opportunities in both rural and urban areas, may lead to improved physical activity and health promotion, particularly among individuals who are more physically inactive.

A decade beyond the economic recession: A study of health-related lifestyles in urban and rural Spain (2006-2017).

The 2008 economic recession may have affected health-related indicators differently depending on the living environment. We analyze health-related indicators in Spain using data from four Spanish health surveys (2006, 2011, 2014, and 2017, 95 924 individuals aged ≥16 years). In 2006-2011, physical activity decreased among men and women, while in 2006-2017, physical activity only decreased among urban women. Daily vegetable intake, except in rural women, increased in 2006-2011 but decreased in 2006-2017 in all groups. Smoking decreased among urban women in 2006-2011 and 2006-2014 but only decreased among men, and even increased among rural women, in 2006-2017. In 2006-2017, obesity increased among men and urban women, good self-rated health status increased in all groups and flu vaccination declined. Blood pressure and cholesterol control decreased in urban women in 2006-2011 but increased in 2006-2017 in all groups, as well as mammographic and cytological control. Our findings highlight the differential impact of the economic recession on health-related lifestyles according to sex and place of residence, underscoring the need for targeted health policies to address evolving health disparities over time.

Spectroscopy and Scattering Studies Using Interpolated Ab Initio Potentials.

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, (H2O)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.

Theoretical study of the CO2-O2 van der Waals complex: potential energy surface and applications.

A four-dimensional-potential energy surface (4D-PES) of the atmospherically relevant carbon dioxide-oxygen molecule (CO2-O2) 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 CO2-O2 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 CO2-X van der Waals complexes. Moreover, we provide a SAPT analysis of this molecular system. Then, we discuss the complexation induced shifts of CO2 and O2. 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 CO2-O2 mixtures.

Ab initio quantum scattering calculations for the CO-O2 system and a new CO-O2 potential energy surface: O2 and air broadening of the R(0) line in CO.

We present ab initio calculations of the collisional broadening of the R(0) pure rotational line in CO (at 115 GHz) perturbed by O2. 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-O2 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 N2 [Józwiak 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.

Gender inequality is associated with gender differences and women participation in physical activity.

BACKGROUND: Living standards determine population's physical activity (PA); however, more women are systemically insufficiently active, suggesting social gender inequality factors. Thus, we assessed the association between gender inequality, PA differences between genders, and total PA. METHODS: We used three independent cross-sectional databases at country-level: PA prevalence (i.e., Active Lifestyle) from the World Health Organization with 1.9 million individuals from 168 countries; daily steps (smartphone registers) of 693 806 people from 46 countries and sport participation in the 2016 Summer Olympics with 11 191 athletes. Gender Inequality Index was used to evaluate aspects surrounding gender equality controlling for overall economic and health status. RESULTS: Higher gender inequality was associated with gender differences in PA (Active Lifestyle, 0.402, P < 0.001; Steps, 0.542, P < 0.001; Olympic participation, 0.346, P = 0.001). Likewise, lower gender inequality was associated with increased women activity (Active Lifestyle, -0.838, P < 0.001; Steps, -0.81, P < 0.001; Olympic participation, -0.577, P < 0.001), and men activity (Active Lifestyle, -0.453, P < 0.001; Steps, -0.461, P = 0.002). CONCLUSIONS: Lower women PA levels could be influenced by gender inequality. Public health policies aimed to improve women living conditions which may promote their participation in PA and sport.

Analysis of Intensities Using Inertial Motion Devices in Female Soccer: Do You Train like You Compete?

Intensity research in female soccer is limited. This study aimed to investigate whether female professional soccer players train with external and internal intensities similar to those recorded in real competition. The specific players' position, the game situation and training task type were analyzed in a total of 18 female players (26.25 ± 3.89 years). The empirical, descriptive and associative study was structured into two parts. Part 1: characterizing the training sessions (n = 13) and official matches (n = 3) using the Integral Analysis System of Training Tasks. The association between sports planning variables was evaluated using adjusted standardized residuals from contingency tables, Chi-Square and Fisher tests, as well as the Phi and Cramer's V coefficients. The main findings show that the coach and/or physical trainer predominantly planned training sessions using small-sided games, which integrate physical fitness and tactical-technical behaviors of the game and imply a medium-high subjective external intensity (20.63 ± 5.79 points). The subjective external intensity of the matches was very high (30.00 ± 0.00 points). Part 2: quantifying the external and internal intensity through the inertial motion devices and heart rate monitors. Differences in the intensities according to the type of session (training session and match), specific position of the players, game situation and type of the training task were assessed through different statistical tests. By specific position (Kruskal-Wallis H and one-factor ANOVA tests), defenders performed fewer accelerations/min and decelerations/min, while they recorded higher heart rates in training sessions and official matches. In contrast, the wingbacks performed higher accelerations/min and decelerations/min in training sessions and official matches. The wingers had the lowest heart rate in official matches. Regarding the game situation (Kruskal-Wallis H test) measured during training sessions, the unopposed tasks recorded higher accelerations/min and decelerations/min, while the small-sided games and full games recorded higher values in the rest of the intensities (both subjective and objective). With regard to the type of training task (Kruskal-Wallis H test), the simple application exercises recorded higher accelerations/min and decelerations/min. Distance in meters/min was greater in the complex application exercises. High-intensity activity/min and player load/min were higher in the simple specific game. In addition, modified sport and real game recorded higher subjective external intensity*min, sprints/min and heart rate. Furthermore, training sessions differed statistically (Mann-Whitney U test) from official matches in terms of subjective intensity and the objective external and internal intensity variables weighted by minutes. For all these reasons, female players do not train (training sessions) as they compete (official matches). The use of inertial motion devices has made it possible to quantify intensities during training sessions and real competition in soccer.

MES SV40 Cells Are Sensitive to Lipopolysaccharide, Peptidoglycan, and Poly I:C Expressing IL-36 Cytokines.

Mesangial cells (MC) maintain the architecture and cellular communication and indirectly join in the glomerular filtration rate for the correct functioning of the glomerulus. Consequently, these cells are activated constantly in response to changes in the intraglomerular environment due to a metabolic imbalance or infection. IL-36, a member of the IL-1 family, is a cytokine that initiates and maintains inflammation in different tissues in acute and chronic pathologies, including the skin, lungs, and intestines. In the kidney, IL-36 has been described in the development of tubulointerstitial lesions, the production of an inflammatory environment, and is associated with metabolic and mesangioproliferative disorders. The participation of IL-36 in functional dysregulation and the consequent generation of the inflammatory environment by MCs in the presence of microbial stimulation is not yet elucidated. In this work, the MES SV40 cell cultures were stimulated with classical pathogen-associated molecular patterns (PAMPs), mimicking an infection by negative and positive bacteria as well as a viral infection. Lipopolysaccharide (LPS), peptidoglycan (PGN) microbial wall components, and a viral mimic poly I:C were used, and the mRNA and protein expression of the IL-36 members were assessed. We observed a differential and dose-dependent IL-36 mRNA and protein expression under LPS, PGN, and poly I:C stimulation. IL-36ß was only found when the cells were treated with LPS, while IL-36α and IL-36γ were favored by PGN and poly I:C stimulation. We suggest that the microbial components participate in the activation of MCs, leading them to the production of IL-36, in which a specific member may participate in the origin and maintenance of inflammation in the glomerular environment that is associated with infections.

Inelastic scattering in isotopologues of O2-Ar: the effects of mass, symmetry, and density of states.

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.

The Low-Lying Electronic States of NO2: Potential Energy and Dipole Surfaces, Bound States, and Electronic Absorption Spectrum.

Nitrogen dioxide, NO2, 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(4Su) and O(3Pg) 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.

Collisional excitation of interstellar PN by H2: New interaction potential and scattering calculations.

Rotational excitation of interstellar PN molecules induced by collisions with H2 is investigated. We present the first ab initio four-dimensional potential energy surface (PES) for the PN-H2 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 H2 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-H2 and para-H2, respectively. Integral cross sections for rotational excitation in PN-H2 collisions were calculated using the new PES and were found to be strongly dependent on the rotational level of the H2 molecule. These new collisional data will be crucial to improve the estimation of PN abundance in the interstellar medium from observational spectra.

Fully quantum calculations of O2-N2 scattering using a new potential energy surface: Collisional perturbations of the oxygen 118 GHz fine structure line.

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 O2 and N2 molecules-the two most abundant atmospheric species. In this work, we report a new highly accurate O2(X3Σg -)-N2(X1Σg +) 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 O2 perturbed by collisions with N2 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.

Computational study of the rovibrational spectrum of CO2-N2.

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.