6533b870fe1ef96bd12d0431

RESEARCH PRODUCT

Perturbative treatment of triple excitations in coupled‐cluster calculations of nuclear magnetic shielding constants

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description

A theory for the calculation of nuclear magnetic shielding constants at the coupled‐cluster singles and doubles level augmented by a perturbative correction for connected triple excitations (CCSD(T)) has been developed and implemented. The approach, which is based on the gauge‐including atomic orbital (GIAO) ansatz, is illustrated by several numerical examples. These include a comparison of CCSD(T) and other highly correlated methods with full configuration interaction for the BH molecule, and a systematic comparison with experiment for HF, H2O,NH3, CH4, N2, CO, HCN, and F2. The results demonstrate the importance of triple excitations in establishing quantitative accuracy. Finally, the ability of GIAO‐CCSD(T) to make accurate predictions for difficult cases is explored in calculations for formaldehyde (CH2O), diazomethane(CH2NN), and ozone (O3).