Entropic Effects on the Aqueous Microsolvation of Protonated Glycine and Protonated β-Alanine. Hybrid Density Functional Theory Born-Oppenheimer Molecular Dynamics Studies.

Abstract

Recent low-temperature infrared-based experimental studies provided information about the effects of aqueous microsolvation on the intramolecular hydrogen bond of protonated glycine and β-alanine [J. Phys. Chem. A 2019, 123, 3355]. Here we address the temperature-dependent entropic effects on the aqueous microsolvation patterns of these protonated amino acids using the AAH+(H2O)n (n = 1-8) cluster model at 50 K and room temperature with Born-Oppenheimer molecular dynamics using a calibrated hybrid density functional. The CCOOH-Ow, N-Ow, and center-of-mass-Ow radial distribution functions provide accurate structural data and temperature-dependent water coordination numbers vs. solvation degree. The solvation patterns for protonated glycine at 50 K show structural features in agreement with previous static optimizations. However, entropic effects at room temperature play a crucial role in the evolution of the intramolecular HB strength vs. solvation degree for both protonated amino acids. With increasing hydration entropic effects favor the making of solvent hydrogen bond networks over full solvation of protonated glycine. At room temperature four water molecules are needed to build the first solvation shell for protonated glycine while five are required for protonated β-alanine. A new statistical Cumulative Percentage of Structures (CPS) scheme is proposed; when the CPS data are analyzed in light of the empirical formula of Rozenberg et al. [Phys. Chem. Chem. Phys. 2000, 2, 2699] and the hydrogen bond relative strength (HBRS) criteria of Jeffrey [An Introduction to Hydrogen Bonding; Oxford University: 1997] we can provide a detailed molecular mechanism for the weakening of the intramolecular hydrogen bond based on the average dynamical structures, which clearly reveals the temperature dependence of this process. The new CPS-HBRS scheme proposed here can be utilized using any type of molecular dynamics trajectory (classical, BOMD, CPMD, etc.).