AuX (X=O, S)低电子态的理论研究

doi:10.3866/PKU.WHXB201405302

Abstract

Abstract:

Multireference approaches have commonly been employed to calculate low-lying states of openshell molecules with spin-orbit coupling (SOC), such as for AuO and AuS. However, by choosing a proper reference state, the equation-of-motion coupled-cluster approach (EOM-CC) can also be used to calculate some low-lying states of these molecules. Furthermore, the EOM-CC approach is a single-reference method and, therefore, more easily employed than multireference approaches. In this work, low-lying states of AuO and AuS are investigated based on a recently developed EOM-CC approach for ionization potentials (EOMIP-CC) with SOC at the CCSD level, using the corresponding anions as reference. The contribution of triples with EOMIPCC is estimated by comparing results of EOMIP-CCSD and EOMIP-CCSDT at a scalar relativistic level. In addition, compared with the EOMIP-CCSDT results, errors by UCCSD(T) can reach 0.1-0.15 eV when spin contamination is significant and the norm of T₁ is sizeable. When SOC is present, bond lengths and harmonic frequencies obtained with EOMIP-CCSD for the investigated states are in reasonable agreement with experimental data. Furthermore, ionization energies corresponding to the high-lying ²Δ_3/2, ²Σ_1/2⁺, and ²Π_1/2 states are overestimated by EOMIP-SOC-CCSD, but results for the other low- lying states agree well with the experimental data, with an error of approximately 0.2 eV. These results indicate that the single-reference EOMIPCCSD method with SOC is able to provide a reasonable description of low-lying states of AuO and AuS.

Key words: Spin-orbit coupling, Equation-of-motion coupled-cluster approach, Ionization energy

MSC2000:

O641

LIANG Yan-Ni, WANG Fan. Theoretical Studies on Low-Lying States of AuX (X=O, S)[J].Acta Phys. -Chim. Sin., 2014, 30(8): 1447-1455.

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Theoretical Studies on Low-Lying States of AuX (X=O, S)

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