The equilibrium structure of propadienylidene

被引:30
作者
Gauss, J
Stanton, JF [1 ]
机构
[1] Univ Texas, Dept Chem, Inst Theoret Chem, Austin, TX 78712 USA
[2] Univ Texas, Dept Biochem, Inst Theoret Chem, Austin, TX 78712 USA
[3] Univ Mainz, Inst Phys Chem, D-55099 Mainz, Germany
基金
美国国家科学基金会;
关键词
propadienylidene; electron correlation; Dunning's basis set;
D O I
10.1016/S0022-2860(99)00084-8
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
A coupled-cluster study of the equilibrium geometry of propadienylidene (C(3)H(2)) is presented. Deviations between a recently reported experimental r(e) structure and those computed at the CCSD(T)/cc-pVQZ and CCSD(T)/cc-pCVQZ levels are larger than expected. A closer analysis reveals that this discrepancy is due to inaccuracies in the cubic force field that was used to correct the measured rotational constants for vibrational effects. A satisfactory agreement between theory and experiment is obtained if the vibrational effects on the rotational constants are computed from harmonic and cubic force fields determined at either the CCSD(T)/cc-pVTZ and CCSD(T)/cc-pCVTZ levels. Revised values for the "experimental" r(e) structure of propadienylidene are also given. (C) 1999 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:43 / 50
页数:8
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