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Post-Hartree-Fock and DFT level studies on the Cl2CO … Cl2 complex: Accurate molecular parameters, harmonic vibrational frequencies, and interaction energies

✍ Scribed by Andrzej Nowek; Jerzy Leszczýnski


Publisher
John Wiley and Sons
Year
1996
Tongue
English
Weight
497 KB
Volume
60
Category
Article
ISSN
0020-7608

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✦ Synopsis


The C1,CO ... C1, complex was studied using ab initio post-Hartree-Fock theory at the MP2 and MP4 levels and, for comparison, the DFT method with 6-311G(2d), 6-311 + G(2d), and Sadlej's medium-size polarized (MSPBS) basis sets. A potential energy search recovered a planar minimum-energy structure characterized by a bent conformation. For this weakly bound complex, the interaction energy corrected for the basis set superposition error amounted to -0.88, -1.09, -1.43, and -0.38 kcal/mol at the MP4(SDTQ)/6-311G(2 d), MPNSDTQ)/6311 + G(2 4, MP4(SDTQ)/MSPBS, and DFT(Becke3LYP)/6-311 + G(2d) levels of theory, respectively. Two highly symmetrical forms, linear and T-shaped, correspond to transition-state conformers. The analysis of harmonic vibrational frequencies and potential energy distribution was performed at the MP2 and DFT levels with the 6-311 + G(2d) basis set. 0 1996 John Wiley & Sons, Inc. reliable predictions for larger systems. The molecular complexes formed with CO group-containing species are among such model compounds and, consequently, have been intensively investigated, both experimentally and t h ~r & ~l l y .

Many studies have focused on very weak interactions of carbon monoxide with HF [l] and H,O . Also, the H,O ... 2co complex was investigated; its spectrum in solid argon was recorded [3a] and a computational study on its molecular structure at