New Density Functional Methods to Compute Molecular Spectra: Local Hybrid Functionals, Magnetic Resonance, and more

This talk will cover various recent developments of modern DFT methods to compute molecular
spectra and to use these for structure assignments. NMR and EPR are central spectroscopic methods
we work with. I will give examples on relativistic computations of NMR chemical shifts for
diamagnetic systems that include sometimes dramatic spin-orbit effects. 1 Recent progress on assigning
local and global structures of paramagnetic metalloenzymes by a combination of state-of-the-art solid-
state NMR and computations 2 will be discussed, as will be the extension to NMR shifts of
paramagnetic solids, with focus on lithium ion battery materials. 3 The exchange-correlation functional
is critical for the accuracy of computed spectroscopic parameters. Here our efforts center on the
development of local hybrid functionals, which feature position-dependent admixture of Hartree-Fock
exchange and show promise for energetics as well as a wide variety of spectroscopic parameters. 4 I
will focus on results for NMR parameters, 5 but also on TDDFT computations of excited-state
properties, 6 with application to singlet fission.