Relativistic effects such as contraction of inner-shell electrons and angular momentum couplings such as the spin-orbit interaction are known to become more important with increasing nuclear charge. For transition metals, these effects are perhaps most noticable in detailed spectroscopic measurements. One way to approximately treat relatvistic effects in ab initio calculations is by using effective core potentials and perturbation theory. Such approaches do not use a relativistic Hamiltonian, but modify the non-relativistic one to mimic the effects. On the other hand, all-electron relativistic calculations that incorporate the correct physics are inherently much more expensive. However, recent advances have made calculations involving moderately-sized transition metal complexes possible. Calculations on a variety of transition metal complexes using relativistic methods such as X2C are compared with their non-relativistic counterparts. The differences in spectra and other observables are discussed.

When should we use relativistic methods for transition metals?

2019 Fall National Meeting

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