Spatial Decay and Limits of Quantum Solute-Solvent Interactions

Abstract

Molecular excitations in the liquid-phase environment are renormalized by the surrounding solvent molecules. Herein, we employ the GW approximation to investigate the solvation effects on the ionization energy of phenol in various solvent environments. The electronic effects differ by up to 0.4 eV among the five investigated solvents. This difference depends on both the macroscopic solvent polarizability and the spatial decay of the solvation effects. The latter is probed by separating the electronic subspace and the GW correlation self-energy into fragments. The fragment correlation energy decays with increasing intermolecular distance and vanishes at ~9 angstroms, and this pattern is independent of the type of solvent environment. The 9 angstrom cutoff defines an effective interacting volume within which the ionization energy shift per solvent molecule is proportional to the macroscopic solvent polarizability. Finally, we propose a simple model for computing the ionization energies of molecules in an arbitrary solvent environment.

References in corpus (8)

• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• Cubic scaling $GW$: towards fast quasiparticle calculations
• Towards GW Calculations on Thousands of Atoms
• Low-scaling $GW$ with benchmark accuracy and application to phosphorene nanosheets
• GPU Acceleration of Large-Scale Full-Frequency GW Calculations
• Theory and applications of generalized Pipek--Mezey Wannier functions
• Efficient treatment of molecular excitations in the liquid phase environment via stochastic many-body theory
• Improving the efficiency of $G_0{W}_0$ calculations with approximate spectral decompositions of dielectric matrices

Cited by in corpus (1)

• Many-body $GW$ calculations with very large scale polarizable environments made affordable: a fully ab initio QM/QM approach