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Insights into the dynamics of evaporation and proton migration in protonated water clusters from Large‐scale Born–Oppenheimer direct dynamics
Author(s) -
Rybkin Vladimir V.,
Simakov Anton O.,
Bakken Vebjørn,
Reine Simen,
Kjærgaard Thomas,
Helgaker Trygve,
Uggerud Einar
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23162
Subject(s) - solvation , molecular dynamics , proton , born–oppenheimer approximation , scaling , chemical physics , chemistry , cluster (spacecraft) , solvation shell , protonation , molecule , diabatic , physics , molecular physics , atomic physics , computational chemistry , thermodynamics , geometry , quantum mechanics , mathematics , computer science , programming language , ion , organic chemistry , adiabatic process
Large‐scale on‐the‐fly Born–Oppenheimer molecular dynamics simulations using recent advances in linear scaling electronic structure theory and trajectory integration techniques have been performed for protonated water clusters around the magic number (H 2 O) n H + , for n = 20 and 21. Besides demonstrating the feasibility and efficiency of the computational approach, the calculations reveal interesting dynamical details. Elimination of water molecules is found to be fast for both cluster sizes but rather insensitive to the initial geometry. The water molecules released acquire velocities compatible with thermal energies. The proton solvation shell changes between the well‐known Eigen and Zundel motifs and is characterized by specific low‐frequency vibrational modes, which have been quantified. The proton transfer mechanism largely resembles that of bulk water but one interesting variation was observed. © 2012 Wiley Periodicals, Inc.