Issue 47, 2013

Nuclear quantum effects on protonated lysine with an asymmetric low barrier hydrogen bond: an ab initio path integral molecular dynamics study

Abstract

The nuclear quantum effect on the short and asymmetric hydrogen bond of protonated lysine (LysH+) at room temperature is explored by ab initio path integral molecular dynamics (PIMD) simulation. From static electronic structure calculations, the barrier height of proton transfer in LysH+ is 1.1 kcal mol−1, which is much lower than that of typical hydrogen bonds. The hydrogen-bonded proton is delocalized in between two nitrogen atoms in the PIMD simulation including both thermal and nuclear quantum effects, while the proton is localized on a nitrogen atom in a conventional ab initio molecular dynamics simulation including thermal effects alone. We found that the proton transfer barrier found in the static calculation and conventional ab initio simulation is completely washed out in the PIMD simulation. Meanwhile, the proton distribution at the Nζ atom was larger than that at the N atom, as found in the static calculation and conventional ab initio molecular dynamics simulation. We clarified that an asymmetric low barrier hydrogen bond exists in LysH+ at room temperature from our PIMD simulation.

Graphical abstract: Nuclear quantum effects on protonated lysine with an asymmetric low barrier hydrogen bond: an ab initio path integral molecular dynamics study

Article information

Article type
Paper
Submitted
01 Aug 2013
Accepted
25 Sep 2013
First published
30 Sep 2013

RSC Adv., 2013,3, 25252-25257

Nuclear quantum effects on protonated lysine with an asymmetric low barrier hydrogen bond: an ab initio path integral molecular dynamics study

Y. Ogata, M. Daido, Y. Kawashima and M. Tachikawa, RSC Adv., 2013, 3, 25252 DOI: 10.1039/C3RA44077J

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