Speaker
Prof.
Thomas Kuhne
(University of Paderborn)
Description
A new energy decomposition analysis for periodic
systems
based on absolutely localized molecular orbitals is
presented [1, 2]. In combination with the recently
developed
”Car-Parrinello-like approach to Born-Oppenheimer MD”
[3]
this not only allows for ab initio molecular dynamics
simulations on previously inaccessible time and length
scales, but also provide unprecedented insights into the
nature of hydrogen bonding between water molecules.
The
effectiveness of this new combined approach is
demonstrated
on liquid water and the water/air interface [4, 5]. Our
simulations reveal that although a water molecule forms,
on
average, two strong donor and two strong acceptor
bonds,
there is a significant asymmetry in the energy of these
contacts. We demonstrate that this asymmetry is a
result of
small instantaneous distortions of hydrogen bonds and
show
that the distinct features of the X-ray absorption spectra
originate from molecules with high instantaneous
asymmetry
[1, 2, 6, 7].
[1] T. D. Kuhne and R. Z. Khaliullin, Nature Comm. 4,
1450
(2013).
[2] R. Z. Khaliullin and T. D. Kuhne, Phys. Chem. Chem.
Phys. 15, 15746 (2013).
[3] T. D. Kuhne, M. Krack, F. Mohamed and M. Parrinello,
Phys. Rev. Lett. 98, 066401 (2007).
[4] T. D. Kuhne, M. Krack and M. Parrinello, J. Chem.
Theory
Comput. 5, 235 (2009).
[5] T. D. Kuhne, T. A. Pascal, E. Kaxiras and Y. Jung, J.
Phys. Chem. Lett. 2, 105 (2011).
[6] C. Zhang, R. Z. Khaliullin, D. Bovi, L. Guidoni and T.
D. Kuhne, J. Chem. Phys. Lett. 4, 3245 (2013)
[7] R. Z. Khaliullin and T. D. Kuhne, J. Am. Chem. Soc.
136,
3395 (2014).
