On the validity of the equivalent cores approximation for computing X-ray photoemission and photoabsorption spectral bands

被引:61
作者
Plashkevych, O
Privalov, T
Ågren, H
Carravetta, V
Ruud, K
机构
[1] Royal Inst Technol, Dept Theoret Chem, S-10044 Stockholm, Sweden
[2] CNR, Ist Chim Quantist & Energet Mol, Area Ric Pisa, I-56010 Pisa, Italy
[3] Univ Calif San Diego, San Diego Supercomp Ctr, La Jolla, CA 92093 USA
关键词
D O I
10.1016/S0301-0104(00)00171-3
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
We evaluate the performance of the equivalent cores (Z + 1) approximation for computing core photoemission and photoabsorption spectral bands versus full self-consistent field optimizations. Franck-Condon factors are obtained using the linear coupling model with the multi-dimensional vibronic coupling constants computed from analytical calculations of the ground state frequencies and normal coordinates, and excited state energy gradients evaluated at the ground state equilibrium geometry. We use carbon monoxide, formaldehyde, chloromethanes and some monosubstituted benzenes for the purpose. Considering other inherent approximations in the calculations, we find that the equivalent core model works well for band shapes and comparatively better for excitations of strong modes and ionization of deeper core levels. The approximation also works somewhat better for photoemission than for discrete photoexcitation. (C) 2000 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:11 / 28
页数:18
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