Photoelectron spectroscopy and photoelectron imaging experiments provide a wealth of information about the electronic structure of molecules and ions in gas phase or in solution, but their interpretation often relies on simple theoretical models with many approximations. We have shown that it is possible to derive photoelectron spectra and photoelectron angular distributions (PADs) from Dyson orbitals computed by an <i>ab initio</i> approach, the equation-of-motion coupled-cluster (EOM-CC) method, which includes both correlation and orbital relaxation effects that are missing in the more basic Hartree-Fock (HF) / Koopmans approach. Dyson orbitals contain all the necessary information about the initial (N electron) wavefunction and the final (N-1 electron) wavefunction of the core. Here, we show that this methodology can be used to study the photoionization of water both in gas phase and in bulk. To model the latter, EOM-CC Dyson orbitals are computed in a hybrid quantum mechanical / molecular mechanical (QM/MM) scheme where the MM part is described using an effective fragment potential (EFP).

Photoionization of water in gas phase and in bulk: Insight from equation-of-motion coupled-cluster Dyson orbitals

249th National Meeting (2015)

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