Ab initio exploration of low-lying electronic states of linear and bent MNX + (M = Ca, Sr, Ba, Ra; X = O, S, Se, Te, Po) and their origins.

Autor: Ariyarathna IR; Physics and Chemistry of Materials (T-1), Los Alamos National Laboratory, Los Alamos, New Mexico, USA.
Jazyk: angličtina
Zdroj: Journal of computational chemistry [J Comput Chem] 2024 Nov 15; Vol. 45 (30), pp. 2530-2538. Date of Electronic Publication: 2024 Jul 09.
DOI: 10.1002/jcc.27456
Abstrakt: High-level multireference and coupled cluster quantum calculations were employed to analyze low-lying electronic states of linear-MNX + and side-bonded-M[NX] + (M = Ca, Sr, Ba, Ra; X = O, S, Se, Te, Po) species. Their full potential energy curves (PECs), dissociation energies (D e s), geometric parameters, excitation energies (T e s), and harmonic vibrational frequencies (ω e s) are reported. The first three chemically bound electronic states of MNX + and M[NX] + are 3 ∑ - , 1 Δ, 1 ∑ + and 3 A″, 1 A', 1 A″, respectively. The 3 ∑ - , 1 Δ, 1 ∑ + of MNX + originate from the M + ( 2 D) + NX( 2 Π) fragments, whereas the 3 A″, 1 A', 1 A″ states of M[NX] + dissociate to M + ( 2 S) + NX( 2 Π) as a result of avoided crossings. The MNX + and M[NX] + are real minima on the potential energy surface and their interconversions are possible. The M 2+ NX - /M 2+ [NX] - ionic structure is an accurate representation for their low-lying electronic states. The D e s of MNX + species were found to depend on the dipole moment (μ) of the corresponding NX ligands and a linear relationship between these two parameters was observed.
(© 2024 The Author(s). Journal of Computational Chemistry published by Wiley Periodicals LLC.)
Databáze: MEDLINE
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