Iterative and non-iterative triple excitation corrections in coupled-cluster methods for excited electronic states: The EOM-CCSDT-3 and EOM-CCSD((T)over-tilde) methods

被引:218
作者
Watts, JD
Bartlett, RJ
机构
[1] Quantum Theory Project, University of Florida, 362 Williamson Hall, Gainesville
关键词
D O I
10.1016/0009-2614(96)00708-7
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
New iterative and non-iterative triple excitation corrections to EOM-CCSD are presented based upon the CCSDT-3 method. This method is recommended formally, since it fully employs the EOM-CCSD Hamiltonian (H) over tilde = exp[-(T-1 + T-2)]Hexp(T-1 + T-2) in its development. This permits defining iterative EOM-CCSDT-3 and non-iterative (<EOM-CCSD (T)over tilde>) corrections correct through second-order in (H) over tilde. Results for some full CI examples demonstrate average errors of 0.09 eV and 0.08 eV, respectively. We also study trans-butadiene as a more demanding example. We also consider a computationally simpler but accurate approximation to (<EOM-CCSD (T)over tilde>), EOM-CCSD(T').
引用
收藏
页码:581 / 588
页数:8
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