Open AccessПрирода тонкой структуры вращательных уровней основного X-=SUP=-2-=/SUP=-Sigma-=SUP=-+-=/SUP=--состояния радикала CN
Author(s) -
В.А. Терашкевич,
Е.А. Пазюк
Publication year - 2021
Publication title -
optika i spektroskopiâ
Language(s) - English
Resource type - Journals
eISSN - 2782-6694
pISSN - 0030-4034
DOI - 10.21883/os.2021.01.50433.210-20
Subject(s) - excited state , quantum number , atomic physics , hamiltonian (control theory) , ab initio , ground state , intramolecular force , ab initio quantum chemistry methods , rotational–vibrational spectroscopy , chemistry , molecule , physics , quantum mechanics , mathematical optimization , mathematics
By means of ab initio high-level quantum-chemical calculations of non-diagonal matrix elements of spin-orbital and electron-rotational coupling between the ground X2Σ+ and excited (1--4)2Π states the observed regular effect of γ-doubling of the rotational levels of the X2Σ+ state was shown to be mainly determined by intramolecular interactions of the mentioned state with remote states (2--4)2Π. In terms of the nonadiabatic model of the effective radial Hamiltonian of the isolated electronic state, it was possible to create the analytical potential of the X2Σ+ state and the corresponding function γ (R) reproducing the frequencies of rotational and vibrational-rotational transitions (for the lowest vibrational levels ν≤3) of the CN molecule at the experimental (spectroscopic) level of accuracy.