Approximating electronically excited states with equation-of-motion linear coupled-cluster theory

作者：Byrd Jason N^*; Rishi Varun; Perera Ajith; Bartlett Rodney J

来源：Journal of Chemical Physics, 2015, 143(16): 164103.

DOI：10.1063/1.4934232

A new perturbative approach to canonical equation-of-motion coupled-cluster theory is presented using coupled-cluster perturbation theory. A second-order Moller-Plesset partitioning of the Hamiltonian is used to obtain the well known equation-of-motion many-body perturbation theory equations and two new equation-of-motion methods based on the linear coupled-cluster doubles and linear coupled-cluster singles and doubles wavefunctions. These new methods are benchmarked against very accurate theoretical and experimental spectra from 25 small organic molecules. It is found that the proposed methods have excellent agreement with canonical equation-of-motion coupled-cluster singles and doubles state for state orderings and relative excited state energies as well as acceptable quantitative agreement for absolute excitation energies compared with the best estimate theory and experimental spectra.

• 出版日期2015-10-28