title: Potential energy surface of the CO2-N2 van der Waals complex.
abstract: 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.
authors.affiliation: Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis, Tunisia.
authors.forename: Sameh
authors.initials: S
authors.lastname: Nasri
authors.affiliation: Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis, Tunisia.
authors.forename: Yosra
authors.initials: Y
authors.lastname: Ajili
authors.affiliation: Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis, Tunisia.
authors.forename: Nejm-Eddine
authors.initials: NE
authors.lastname: Jaidane
authors.affiliation: Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050, Russia.
authors.forename: Yulia N
authors.initials: YN
authors.lastname: Kalugina
authors.affiliation: Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Halvick
authors.affiliation: Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Stoecklin
authors.affiliation: Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, France.
authors.forename: Majdi
authors.initials: M
authors.lastname: Hochlaf
mesh_terms: D016880:Anisotropy; D002245:Carbon Dioxide / Q000737:chemistry*; D019281:Dimerization; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry*
chemical_list: D002245:Carbon Dioxide; D009584:Nitrogen