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

TL;DR

This paper introduces an efficient computational method combining algebraic diagrammatic construction theory with polarizable embedding to accurately simulate ionized electronic states in complex chemical environments, validated by thymine in water.

Contribution

The novel PE-IP-ADC approach enables accurate simulation of ionized states in condensed-phase environments, addressing challenges of electron correlation and environmental interactions.

Findings

PE-IP-ADC accurately predicts solvent-induced shifts in ionization energy.

Second- and third-order PE-IP-ADC methods agree well with experimental data.

Method demonstrates potential for studying charged states in realistic environments.

Abstract

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-zeta 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.