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MRCI investigations on dissociation energy and molecular constants of BCl(X 1 Σ + ) radical
Author(s) -
Shi DeHeng,
Liu Hui,
Zhang XiaoNiu,
Sun JinFeng,
Liu YuFang,
Zhu ZunLue
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22699
Subject(s) - multireference configuration interaction , atomic physics , bond dissociation energy , dissociation (chemistry) , valence (chemistry) , basis set , chemistry , potential energy , quantum number , physics , configuration interaction , molecule , quantum mechanics , excited state
The equilibrium internuclear separations and harmonic frequencies of the BCl(X 1 Σ + ) radical have been studied using the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in combination with a series of correlation‐consistent basis sets in the valence range. To accurately determine the ground‐state dissociation energy of the radical, the potential energy curve (PEC) is calculated at each basis set over the internuclear distance range from about 0.08 to 2.00 nm so as to affirm that the PEC is completely smooth and convergent. The PECs are all fitted to the Murrell‐Sorbie function form, which are employed to reproduce the spectroscopic parameters, such as ω e χ e , α e , B e , and D 0 . The present D 0 , D e , R e , ω e , ω e χ e , α e , and B e obtained at the MRCI/aug‐cc‐pV5Z level of theory with the relativistic corrections are of 5.2906 eV, 5.3429 eV, 0.1713 nm, 845.70 cm −1 , 5.3828 cm −1 , 0.006684 cm −1 , and 0.6860 cm −1 , respectively, which almost perfectly conform to the available measurements. The effects on the spectroscopic parameters by the relativistic corrections at different basis sets have been taken into considerations. With the potential determined at the MRCI/aug‐cc‐pV5Z level of theory, which considers the relativistic corrections, a total of 90 vibrational states is predicted when the rotational quantum number J equals zero ( J = 0) by numerically solving the radial Schrödinger equation of nuclear motion. For each vibrational state, one vibrational level and corresponding classical turning points, one inertial rotation and six centrifugal distortion constants are determined when J = 0, which are in excellent agreement with the available experimental data. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011