ON THE GEOMETRICAL STRUCTURE OF THE C-3+ CATION - AN ABINITIO STUDY

被引:30
作者
MARTIN, JML [1 ]
FRANCOIS, JP [1 ]
GIJBELS, R [1 ]
机构
[1] UNIV INSTELLING ANTWERP, INST MAT SCI, DEPT CHEM, B-2610 WILRIJK, BELGIUM
关键词
D O I
10.1063/1.458641
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The potential energy surface of the C3+ cation has been investigated using coupled cluster techniques and large basis sets. The results are particularly sensitive towards the level of electron correlation. Spin contamination even produces a "false stationary point" at the UHF/ 6-31G* level. C3+ has a cyclic 2B2 ground state with predicted geometry r = 1.3242 Å, θ = 73.06° (MP2/6-311G*, empirically corrected bond distance). At the highest level of theory considered, the linear structure (2Σu+ state) lies about 2 kcal/mol above the ground state: this might imply quasilinearity. There is also a low barrier towards degenerate isomerization: at high temperatures, C3 + will be extremely floppy. Harmonic frequencies (UHF/6-31G*) as well as double-harmonic IR and Raman intensities are given for various structures of C3+. Interesting analogies of C 3+ with B3 and B2N are pointed out. The heat of formation at 298.15 K, vertical and adiabatic ionization potentials of C3 are predicted as 194.9 ± 2 kcal/mol, 11.92 ± 0.1 eV, and 11.84 ± 0.1 eV, respectively. © 1990 American Institute of Physics.
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页码:5037 / 5045
页数:9
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