Isotopic effects on the rotational (de-)excitation rate coefficients of ortho-CH3Cl colliding with He.

Chloromethane, CH3Cl, is the first organohalogen molecule to be detected in the interstellar medium. Using the recently generated accurate three-dimensional potential energy surface (3D-PES) for the weakly bound CH335Cl-He complex, we deduced that of CH337Cl-He. Both 3D-PESs were incorporated later into dynamical computations code for nuclear motions treatments of each isotopologue colliding with He. We determined the state-to-state (de-)excitation cross sections for transitions among the 105 lowest rotational levels of both ortho-CH335Cl and ortho-CH337Cl (up to jkɛ = 206±). For total energies up to 100 cm-1, we used the quantum close-coupling methodology, and we adopted the coupled state approach for higher energies (up to 2500 cm-1). Rate coefficients for temperatures ranging from 5 to 150 K are then deduced after averaging these cross sections over a Maxwell-Boltzmann velocity distribution. Computations show that isotopic effects are weak, validating the use of collision rates of ortho-CH335Cl for ortho-CH337Cl and vice-versa. However, we expect that our results will be helpful to accurately determine the abundances of these isotopologues in the interstellar medium and, more generally, for understanding the complex and still not fully elucidated chemistry of chlorine containing molecular species there.

Towards the generation of potential energy surfaces of weakly bound medium-sized molecular systems: the case of benzonitrile-He complex.

Currently, the explicitly correlated coupled cluster method is used routinely to generate the multi-dimensional potential energy surfaces (mD-PESs) of van der Waals complexes of small molecular systems relevant for atmospheric, astrophysical and industrial applications. Although very accurate, this method is computationally prohibitive for medium and large molecules containing clusters. For instance, the recent detections of complex organic molecules (COMs) in the interstellar medium, such as benzonitrile, revealed the need to establish an accurate enough electronic structure approach to map the mD-PESs of these species interacting with the surrounding gases. As a benchmark, we have treated the case of the polar molecule benzonitrile interacting with helium, where we use post-Hartree-Fock and symmetry-adapted perturbation theory (SAPT) techniques. Accordingly, we show that MP2 and distinguishable-cluster approximation (DCSD) cannot be used for this purpose, whereas accurate enough PESs may be obtained using the corresponding explicitly correlated versions (MP2-F12 or DCSD-F12) with a reduction in computational costs. Alternatively, computations revealed that SAPT(DFT) is as performant as CCSD(T)-F12/aug-cc-pVTZ, making it the method of choice for mapping the mD-PESs of COMs containing clusters. Therefore, we have used this approach to generate the 3D-PES of the benzonitrile-He complex along the intermonomer Jacobi coordinates. As an application, we have incorporated the analytic form of this PES into quantum dynamical computations to determine the cross sections of the rotational (de-)excitation of benzonitrile colliding with helium at a collision energy of 10 cm-1.

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.

Potential energy surface of the CO2-N2 van der Waals complex.

Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO2-N2 van der Waals complex is generated using the explicitly correlated coupled cluster with single, double, and perturbative triple excitation (CCSD(T)-F12) method in conjunction with the augmented correlation consistent triple zeta (aug-cc-pVTZ) basis set. This 4D-PES is mapped along the intermonomer coordinates. An analytic fit of this 4D-PES is performed. Our extensive computations confirm that the most stable form corresponds to a T-shape structure where the nitrogen molecule points towards the carbon atom of CO2. In addition, we located a second isomer and two transition states in the ground state PES of CO2-N2. All of them lay below the CO2 + N2 dissociation limit. This 4D-PES is flat and strongly anisotropic along the intermonomer coordinates. This results in the possibility of the occurrence of large amplitude motions within the complex, such as the inversion of N2, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C2v structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

Explicit correlation treatment of the potential energy surface of CO2 dimer.

We present an extensive study of the four-dimensional potential energy surface (4D-PES) of the carbon dioxide dimer, (CO2)2. This PES is developed over the set of intermolecular coordinates. The electronic computations are carried out at the explicitly correlated coupled cluster method with single, double, and perturbative triple excitations [CCSD(T)-F12] level of theory in connection with the augmented correlation-consistent aug-cc-pVTZ basis set. An analytic representation of the 4D-PES is derived. Our extensive calculations confirm that "Slipped Parallel" is the most stable form and that the T-shaped structure corresponds to a transition state. Later on, this PES is employed for the calculations of the vibrational energy levels of the dimer. Moreover, the temperature dependence of the dimer second virial coefficient and of the first spectral moment of rototranslational collision-induced absorption spectrum is derived. For both quantities, a good agreement is found between our values and the experimental data for a wide range of temperatures. This attests to the high quality of our PES. Generally, our PES and results can be used for modeling CO2 supercritical fluidity and examination of its role in planetary atmospheres. It can be also incorporated into dynamical computations of CO2 capture and sequestration. This allows deep understanding, at the microscopic level, of these processes.

On the accuracy of explicitly correlated methods to generate potential energy surfaces for scattering calculations and clustering: application to the HCl-He complex.

We closely compare the accuracy of multidimensional potential energy surfaces (PESs) generated by the recently developed explicitly correlated coupled cluster (CCSD(T)-F12) methods in connection with the cc-pVXZ-F12 (X = D, T) and aug-cc-pVTZ basis sets and those deduced using the well-established orbital-based coupled cluster techniques employing correlation consistent atomic basis sets (aug-cc-pVXZ, X = T, Q, 5) and extrapolated to the complete basis set (CBS) limit. This work is performed on the benchmark rare gas-hydrogen halide interaction (HCl-He) system. These PESs are then incorporated into quantum close-coupling scattering dynamical calculations in order to check the impact of the accuracy of the PES on the scattering calculations. For this system, we deduced inelastic collisional data including (de-)excitation collisional and pressure broadening cross sections. Our work shows that the CCSD(T)-F12/aug-cc-pVTZ PES describes correctly the repulsive wall, the van der Waals minimum and long range internuclear distances whereas cc-pVXZ-F12 (X = D,T) basis sets are not diffuse enough for that purposes. Interestingly, the collision cross sections deduced from the CCSD(T)-F12/aug-cc-pVTZ PES are in excellent agreement with those obtained with CCSD(T)/CBS methodology. The position of the resonances and the general shape of these cross sections almost coincide. Since the cost of the electronic structure computations is reduced by several orders of magnitude when using CCSD(T)-F12/aug-cc-pVTZ compared to CCSD(T)/CBS methodology, this approach can be recommended as an alternative for generation of PESs of molecular clusters and for the interpretation of accurate scattering experiments as well as for a wide production of collisional data to be included in astrophysical and atmospherical models.