Open AccessInvestigations on molecular structure and analytic potential energy function of the AsH(X3Σ-) and AsH2(C2v，X2B1) radicals
Author(s) -
Deheng Shi,
Hui Liu,
Jinfeng Sun,
Zunlue Zhu,
Yufang Liu
Publication year - 2010
Publication title -
wuli xuebao
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.199
H-Index - 47
ISSN - 1000-3290
DOI - 10.7498/aps.59.227
Subject(s) - bond dissociation energy , dissociation (chemistry) , basis set , ab initio , atomic physics , potential energy , materials science , radical , saddle point , bond length , molecular physics , chemistry , physics , computational chemistry , molecule , density functional theory , quantum mechanics , geometry , mathematics , organic chemistry
The CCSD(T) theory in combination with the cc-pV5Z basis set is used to determine the equilibrium geometrydissociation energy and vibrational frequencies of AsH2(C2vX2B1) radical. By comparisonexcellent agreement can be found between the present results and the experiments. The values obtained at present are of 01508 nm for the equilibrium bond length RAs-H912231° for the bond angle ∠HAsH28795 eV for the dissociation energy De(HAs-H) and 10133361 cm-122251347 cm-1 and 22337565 cm-1 for the vibrational frequencies ν1(a1)ν2(a1) and ν3(a1)respectively. The equilibrium geometryharmonic frequency and potential energy curve of the AsH(X3Σ-) radical are calculated at the CCSD(T)/cc-pV5Z level of theory. The ab initio results are fitted to the Murrell-Sorbie function with the least-square method. The spectroscopic parameters are in excellent agreement with the experiments. The analytic potential energy function of the AsH2(C2vX2B1) radical is derived by using the many-body expansion theory. This function correctly describes the configuration and dissociation energy of the AsH2(C2vX2B1) radical. Two symmetrical saddle points have been found at (0160 nm0296 nm) and (0296 nm0160 nm)respectively. And the barrier height is equal to 01512×4184 kJ/mol.