Simulating Ionized States in Realistic Chemical Environments with Algebraic Diagrammatic Construction Theory and Polarizable Embedding

Theoretical simulations of electron detachment processes
are vital
for understanding chemical redox reactions, semiconductor and electrochemical
properties, and high-energy radiation damage. However, accurate calculations
of ionized electronic states are very challenging due to their open-shell
nature, importance of electron correlation effects, and strong interactions
with chemical environment. In this work, we present an efficient approach
based on algebraic diagrammatic construction theory with polarizable
embedding that allows to accurately simulate ionized electronic states
in condensed-phase or biochemical environments (PE-IP-ADC). We showcase
the capabilities of PE-IP-ADC by computing the vertical ionization
energy (VIE) of thymine molecule solvated in bulk water. Our results
show that the second- and third-order PE-IP-ADC methods combined with
the basis of set of triple-ζ quality yield a solvent-induced
shift in VIE of −0.92 and −0.93 eV, respectively, in
an excellent agreement with experimental estimate of −0.9 eV.
This work demonstrates the power of PE-IP-ADC approach for simulating
charged electronic states in realistic chemical environments and motivates
its further development.