TY - JOUR

T1 - Theoretical study of the CO2-O2 van der Waals complex

T2 - potential energy surface and applications

AU - Ajili, Yosra

AU - Quintas-Sánchez, Ernesto

AU - Mehnen, Bilel

AU - Żuchowski, Piotr S.

AU - Brzęk, Filip

AU - El-Kork, Nayla

AU - Gacesa, Marko

AU - Dawes, Richard

AU - Hochlaf, Majdi

N1 - Funding Information:
This study was carried out while M. H. was Visiting Professor at Khalifa University (supported by the internal grant 8474000362-KU-FSU-2021). M. G. is partly supported by Khalifa University (grants 8474000336-KU-SPSC and 8474000362-KU-FSU-2021). N. E. K. is partly supported by Khalifa University (grants 8474000336-KU-SPSC and ASPIRE grant AARE20-031). R. D. and E. Q.-S. were supported by the U.S. Department of Energy (Award No. DE-SC0019740). B. M., P. Z. and F. B. acknowledge the National Science Center for support (Sonata Bis 9, Grant No. 2019/34/E/ST4/00407). We also acknowledge partial support from the Programme National “Physique et Chimie du Milieu Interstellaire” (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES.
Publisher Copyright:
© 2022 The Royal Society of Chemistry.

PY - 2022/11/17

Y1 - 2022/11/17

N2 - 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 - 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.

UR - http://www.scopus.com/inward/record.url?scp=85142676958&partnerID=8YFLogxK

U2 - 10.1039/d2cp04101d

DO - 10.1039/d2cp04101d

M3 - Article

C2 - 36420625

AN - SCOPUS:85142676958

SN - 1463-9076

VL - 24

SP - 28984

EP - 28993

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 47

ER -