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Title: Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex

Abstract

Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} 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 CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} 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 N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.

Authors:
;  [1];  [2];  [1];  [3]; ;  [4];  [5]
  1. Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA, Université de Tunis El Manar, Tunis (Tunisia)
  2. (France)
  3. Department of Optics and Spectroscopy, Tomsk State University, 36 Lenin Ave., Tomsk 634050 (Russian Federation)
  4. Institut des Sciences Moléculaires, Université de Bordeaux, CNRS UMR 5255, 33405 Talence Cedex (France)
  5. Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)
Publication Date:
OSTI Identifier:
22415737
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANISOTROPY; ATOMS; BASES; CALCULATION METHODS; CARBON; CARBON DIOXIDE; COMPLEXES; CORRECTIONS; CORRELATIONS; DISSOCIATION; EXCITATION; FOUR-DIMENSIONAL CALCULATIONS; GROUND STATES; ISOMERS; MOLECULES; NITROGEN; POTENTIAL ENERGY; SURFACES; VAN DER WAALS FORCES

Citation Formats

Nasri, Sameh, Ajili, Yosra, Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, Jaidane, Nejm-Eddine, Kalugina, Yulia N., Halvick, Philippe, Stoecklin, Thierry, and Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr. Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex. United States: N. p., 2015. Web. doi:10.1063/1.4919396.
Nasri, Sameh, Ajili, Yosra, Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, Jaidane, Nejm-Eddine, Kalugina, Yulia N., Halvick, Philippe, Stoecklin, Thierry, & Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr. Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex. United States. doi:10.1063/1.4919396.
Nasri, Sameh, Ajili, Yosra, Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée, Jaidane, Nejm-Eddine, Kalugina, Yulia N., Halvick, Philippe, Stoecklin, Thierry, and Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr. Thu . "Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex". United States. doi:10.1063/1.4919396.
@article{osti_22415737,
title = {Potential energy surface of the CO{sub 2}–N{sub 2} van der Waals complex},
author = {Nasri, Sameh and Ajili, Yosra and Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée and Jaidane, Nejm-Eddine and Kalugina, Yulia N. and Halvick, Philippe and Stoecklin, Thierry and Hochlaf, Majdi, E-mail: hochlaf@univ-mlv.fr},
abstractNote = {Four-dimensional potential energy surface (4D-PES) of the atmospherically relevant CO{sub 2}–N{sub 2} 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 CO{sub 2}. In addition, we located a second isomer and two transition states in the ground state PES of CO{sub 2}–N{sub 2}. All of them lay below the CO{sub 2} + N{sub 2} 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 N{sub 2}, as suggested in the recent spectroscopic experiments. Finally, we show that the experimentally established deviations from the C{sub 2v} structure at equilibrium for the most stable isomer are due to the zero-point out-of-plane vibration correction.},
doi = {10.1063/1.4919396},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}