Performance of the EOMIP-CCSD(2) Method for Determining the Structure and Properties of Doublet Radicals: A Benchmark Investigation

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• 作者：Achintya Kumar Dutta ; Nayana Vaval ; Sourav Pal
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：October 8, 2013
• 年：2013
• 卷：9
• 期：10
• 页码：4313-4331
• 全文大小：425K
• 年卷期：v.9,no.10(October 8, 2013)
• ISSN：1549-9626

文摘

We present a benchmark study on the performance of the EOMIP-CCSD(2) method for computation of structure and properties of doublet radicals. The EOMIP-CCSD(2) method is a second-order approximation to the standard EOMIP-CCSD method. By retaining the black box nature of the standard EOMIP-CCSD method and adding favorable N⁵ scaling, the EOMIP-CCSD(2) method can become the method of choice for predicting the structure and spectroscopic properties of large doublet radicals. The EOMIP-CCSD(2) method overcomes the typical problems associated with the standard single reference ab initio treatment of doublet radicals. We compare our results for geometries and harmonic vibrational frequencies with those obtained using the standard EOMIP-CCSD method, as well as unrestricted Hartree鈥揊ock (UHF)- and restricted open-shell Hartree鈥揊ock (ROHF)-based single-reference coupled-cluster and second order many-body perturbation theory (MBPT(2)) methods. The effect of the basis set on the quality of the results has been studied using a hierarchy of Dunning鈥檚 correlation-consistent aug-cc-pVXZ (X = D, T, Q) basis sets. Numerical results show that the EOMIP-CCSD(2) method, despite its N⁵ scaling, gives better agreement with experimental results, compared to the UHF- and ROHF-based MBPT(2), as well as the single-reference coupled-cluster methods.