Improved Description of Environment and Vibronic Effects with Electrostatically Embedded ML Potentials

Abstract

<span style="color:rgb( 21 , 21 , 21 )">Incorporation of environment and vibronic effects in simulations of optical spectra and excited state dynamics is commonly done by combining molecular dynamics with excited state calculations, which allows to estimate the spectral density describing the frequency-dependent system-bath coupling strength. The need for efficient sampling, however, usually leads to the adoption of classical force fields despite well-known inaccuracies due to the mismatch with the excited state method. Here, we present a multiscale strategy that overcomes this limitation by combining EMLE simulations based on electrostatically embedded ML potentials with the QM/MMPol polarizable embedding model to compute the excited states and spectral density of 3-methyl-indole, the chromophoric moiety of tryptophan that mediates a variety of important biological functions, in the gas phase, in water solution, and in the human serum albumin protein. Our protocol provides highly accurate results that faithfully reproduce their </span><em style="color:rgb( 21 , 21 , 21 )">ab initio</em><span style="color:rgb( 21 , 21 , 21 )"> QM/MM counterparts, thus paving the way for accurate investigations on the interrelation between the time scales of biological motion and the photophysics of tryptophan and other biosystems.</span>