Abstract
Ab initio and Perdew, Burke, and Ernzerhof (PBE) density functional theory with dispersion correction (PBE-D3) calculations are performed to study N2-Arn (n ≤ 3) complexes and N2 trapped in Ar matrix (i.e., N2@Ar). For cluster computations, we used both Møller-Plesset (MP2) and PBE-D3 methods. For N2@Ar, we used a periodic-dispersion corrected model for Ar matrix, which consists on a slab of four layers of Ar atoms. We determined the equilibrium structures and binding energies of N2 interacting with these entities. We also deduced the N2 vibrational frequency shifts caused by clustering or embedding compared to an isolated N2 molecule. Upon complexation or embedding, the vibrational frequency of N2 is slightly shifted, while its equilibrium distance remains unchanged. This is due to the weak interactions between N2 and Ar within these compounds. Our calculations show the importance of inclusion of dispersion effects for the accurate description of geometrical and spectroscopic parameters of N2 isolated, in interaction with Ar surfaces, or trapped in Ar matrices.
Highlights
IntroductionThe study of interactions between rare-gas atoms and molecules provides a wealth of information on molecular properties (matrix spectroscopies, for example) and on how their properties are modified by their environments (i.e. matrix shift) [1]
The study of interactions between rare-gas atoms and molecules provides a wealth of information on molecular properties and on how their properties are modified by their environments [1]
Our results indicate clearly that including the dispersion correction D3 is crucial for the description of the potential energy with Density functional theory (DFT) since it leads to deeper potentials, in agreement with the CCSD(T) results
Summary
The study of interactions between rare-gas atoms and molecules provides a wealth of information on molecular properties (matrix spectroscopies, for example) and on how their properties are modified by their environments (i.e. matrix shift) [1]. It has been shown that if the interaction between the rare-gas atoms and the molecule is weak, the molecular properties are only slightly perturbed by the surrounding environment and are a very close to those of the isolated molecule [2] This condition is satisfied for neutral van der Waals (vdW) complexes containing molecules interacting with rare gas atoms [3]. Such interactions play important roles in several chemical, physical and biological media [3,4,5,6,7,8]. They control the 3D structures of DNA and proteins, crystal packing, aggregates formation, and the orientation of molecules when approaching surfaces [9,10]
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