The small impact of various partial charge distributions in ground and excited state on the computational Stokes shift of 1-methyl-6-oxyquinolinium betaine in diverse water models

TL;DR

This study investigates how different partial charge distributions and water models affect the simulation of the Stokes shift in a specific solute, finding that solvation dynamics are largely independent of charge details but sensitive to water model accuracy.

Contribution

It demonstrates that the solvation relaxation behavior is insensitive to partial charge variations but depends on the water model, emphasizing the importance of including multiple solvation shells for accurate results.

Findings

Different charge calculation methods influence dipole moments but not relaxation behavior.

Polarizable water models match experimental diffusion and viscosity, improving simulation accuracy.

Including at least two solvation shells is necessary for accurate Stokes shift modeling.

Abstract

The influence of the partial charge distribution obtained from quantum mechanics of the solute 1-methyl-6-oxyquinolinium betaine in the ground- and first excited state on the time-dependent Stokes shift is studied via molecular dynamics computer simulation. Furthermore, the effect of the employed solvent model - here the non-polarizable SPC, TIP4P and TIP4P/2005 and the polarizable SWM4 water model - on the solvation dynamics of the system is investigated. The use of different functionals and calculation methods influences the partial charge distribution and the magnitude of the dipole moment of the solute, but not the orientation of the dipole moment. Simulations based on the calculated charge distributions show nearly the same relaxation behavior. Approximating the whole solute molecule by a dipole results in the same relaxation behavior, but lower solvation energies, indicating that the time scale of the Stokes shift does not depend on peculiarities of the solute. However, the SPC and TIP4P water models show too fast dynamics which can be ascribed to a too large diffusion coefficient and too low viscosity. The calculated diffusion coefficient and viscosity for the SWM4 and TIP4P/2005 model coincide well with experimental values and the corresponding relaxation behavior is comparable to experimental values. Furthermore we found that for a quantitative description of the Stokes shift of the applied system at least two solvation shells around the solute have to be taken into account.