Correlated, relativistic, and basis set limit molecular polarizability calculations to evaluate an augmented effective core potential basis set

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AbstractInitial investigations have demonstrated that an augmented ECP basis set can be used to calculate valence electronic properties with deviations of less than 1% from all‐electron basis sets. Past work has largely focused on molecules with relatively light atoms (Z<18) examined with time‐dependent Hartree–Fock (TDHF) theory. In this work, the dipole moment and polarizability of a number of well‐studied molecules are examined with HF, MP2, CCSD, and CCSD(T) correlated wave functions. Additionally, systems not as thoroughly studied due to the difficulty of all‐electron calculations when Z=50–85 are included. The SBK ECP basis set, augmented with optimized valence functions, performs well across a broad range of methods, less than 3% different from all electron relativistic and correlated wave functions. Orders of magnitude time savings (101–104) are exchanged for a minimal difference from all‐electron basis sets. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006