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A4: Understanding Water Relaxation Dynamics at Interfaces

The aim of the project is to develop multiscale approaches to understand the mechanisms of vibrational energy relaxation in water at interfaces and in confined environment. In the first funding period, we have developed an efficient method to describe molecular vibrational relaxation based on single molecule excitations and the use of new descriptors. In the second funding period, we plan to include nuclear quantum effects (NQEs), which may be important in water. We aim to develop a multi resolution scheme where the electronic structure is included with an effective force field, which accurately reproduces high-level ab initio calculations, while the NQEs are explicitly addressed with the path integral formalism.

Role of pH in the synthesis and growth of gold nanoparticles using L-Asparagine: A combined experimental and simulation study
Ricardo Baez, Luis A. Baptista, Samuel Ntim, Paulraj Manidurai, Shirly Espinoza, Charusheela Ramanan, Robinson Cortes-Huerto, Marialore Sulpizi
Journal of Physics: Condensed Matter, (2021);
doi:10.1088/1361-648x/abf6e3

Role of image charges in ionic liquid confined between metallic interfaces
Samuel Ntim, Marialore Sulpizi
Physical Chemistry Chemical Physics 22 (19), 10786-10791 (2020);
doi:10.1039/d0cp00409j

Structure and Dynamics of Solid/Liquid Interfaces
Marie‐Pierre Gaigeot Marialore Sulpizi
Surface and Interface Science: Volume 7: Liquid and Biological Interfaces Volume 7 (Chapter 50), 143-193 (2020);
doi:10.1002/9783527680597.ch50

Surface Charges at the CaF 2 /Water Interface Allow Very Fast Intermolecular Vibrational‐Energy Transfer
Dominika Lesnicki, Zhen Zhang, Mischa Bonn, Marialore Sulpizi, Ellen H. G. Backus
Angewandte Chemie International Edition 59 (31), 13116-13121 (2020);
doi:10.1002/anie.202004686

Oberflächenladungen an der CaF 2 ‐Wasser‐Grenzfläche erlauben eine sehr schnelle intermolekulare Übertragung von Schwingungsenergie
Dominika Lesnicki, Zhen Zhang, Mischa Bonn, Marialore Sulpizi, Ellen H. G. Backus
Angewandte Chemie 132 (31), 13217-13222 (2020);
doi:10.1002/ange.202004686

Heterogeneous Interactions between Gas-Phase Pyruvic Acid and Hydroxylated Silica Surfaces: A Combined Experimental and Theoretical Study
Yuan Fang, Dominika Lesnicki, Kristin J. Wall, Marie-Pierre Gaigeot, Marialore Sulpizi, Veronica Vaida, Vicki H. Grassian
The Journal of Physical Chemistry A 123 (5), 983-991 (2019);
doi:10.1021/acs.jpca.8b10224

Understanding the Acidic Properties of the Amorphous Hydroxylated Silica Surface
Maciej Gierada, Frank De Proft, Marialore Sulpizi, Frederik Tielens
The Journal of Physical Chemistry C 123 (28), 17343-17352 (2019);
doi:10.1021/acs.jpcc.9b04137

Insight into induced charges at metal surfaces and biointerfaces using a polarizable Lennard–Jones potential
Isidro Lorenzo Geada, Hadi Ramezani-Dakhel, Tariq Jamil, Marialore Sulpizi, Hendrik Heinz
Nature Communications 9 (1), (2018);
doi:10.1038/s41467-018-03137-8

Increased Acid Dissociation at the Quartz/Water Interface
Shivam Parashar, Dominika Lesnicki, Marialore Sulpizi
The Journal of Physical Chemistry Letters 9 (9), 2186-2189 (2018);
doi:10.1021/acs.jpclett.8b00686

Dynamical heterogeneities of rotational motion in room temperature ionic liquids evidenced by molecular dynamics simulations
Kota Usui, Johannes Hunger, Mischa Bonn, Marialore Sulpizi
The Journal of Chemical Physics 148 (19), 193811 (2018);
doi:10.1063/1.5005143

A Microscopic Interpretation of Pump–Probe Vibrational Spectroscopy Using Ab Initio Molecular Dynamics
Dominika Lesnicki, Marialore Sulpizi
The Journal of Physical Chemistry B 122 (25), 6604-6609 (2018);
doi:10.1021/acs.jpcb.8b04159

Atypical titration curves for GaAl12 Keggin-ions explained by a joint experimental and simulation approach
Marialore Sulpizi, Johannes Lützenkirchen
The Journal of Chemical Physics 148 (22), 222836 (2018);
doi:10.1063/1.5024201

A set-up for simultaneous measurement of second harmonic generation and streaming potential and some test applications
Johannes Lützenkirchen, Tim Scharnweber, Tuan Ho, Alberto Striolo, Marialore Sulpizi, Ahmed Abdelmonem
Journal of Colloid and Interface Science 529, 294-305 (2018);
doi:10.1016/j.jcis.2018.06.017

Unravelling the GLY-PRO-GLU tripeptide induced reconstruction of the Au(110) surface at the molecular scale
Isidro Lorenzo Geada, Ivan Petit, Marialore Sulpizi, Frederik Tielens
Surface Science 677, 271-277 (2018);
doi:10.1016/j.susc.2018.07.006

Nanophase Segregation of Self-Assembled Monolayers on Gold Nanoparticles
Santosh Kumar Meena, Claire Goldmann, Douga Nassoko, Mahamadou Seydou, Thomas Marchandier, Simona Moldovan, Ovidiu Ersen, François Ribot, Corinne Chanéac, Clément Sanchez, David Portehault, Frederik Tielens, Marialore Sulpizi
ACS Nano 11 (7), 7371-7381 (2017);
doi:10.1021/acsnano.7b03616

π+–π+ stacking of imidazolium cations enhances molecular layering of room temperature ionic liquids at their interfaces
Fujie Tang, Tatsuhiko Ohto, Taisuke Hasegawa, Mischa Bonn, and Yuki Nagata
Phys. Chem. Chem. Phys. 19, 2850 (2017);
URL: http://pubs.rsc.org/is/content/articlehtml/2016/cp/c6cp07034e

The interfacial structure of room temperature ionic liquids (RTILs) controls many of the unique properties of RTILs, such as the high capacitance of RTILs and the efficiency of charge transport between RTILs and electrodes. RTILs have been experimentally shown to exhibit interfacial molecular layering structures over a 10 Å length scale. However, the driving force behind the formation of these layered structures has not been resolved. Here, we report ab initio molecular dynamics simulations of imidazolium RTIL/air and RTIL/graphene interfaces along with force field molecular dynamics simulations. We find that the π+–π+ interaction of imidazolium cations enhances the layering structure of RTILs, despite the electrostatic repulsion. The length scales of the molecular layering at the RTIL/air and RTIL/graphene interfaces are very similar, manifesting the limited effect of the substrate on the interfacial organization of RTILs.

A new force field including charge directionality for TMAO in aqueous solution
Kota Usui, Yuki Nagata, Johannes Hunger, Mischa Bonn and Marialore Sulpizi
J. Chem. Phys. 145, 064103 (2016);
doi:10.1063/1.4960207

We propose a new force field for trimethylamine N-oxide (TMAO), which is designed to reproduce the long-lived and highly directional hydrogen bond between the TMAO oxygen (OTMAO) atom and surrounding water molecules. Based on the data obtained by ab initio molecular dynamics simulations, we introduce three dummy sites around OTMAO to mimic the OTMAO lone pairs and we migrate the negative charge on the OTMAO to the dummy sites. The force field model developed here improves both structural and dynamical properties of aqueous TMAO solutions. Moreover, it reproduces the experimentally observed dependence of viscosity upon increasing TMAO concentration quantitatively. The simple procedure of the force field construction makes it easy to implement in molecular dynamics simulation packages and makes it compatible with the existing biomolecular force fields. This paves the path for further investigation of protein-TMAO interaction in aqueous solutions.

Molecular Dynamics Simulations of SFG Librational Modes Spectra of Water at the Water–Air Interface
Rémi Khatib, Taisuke Hasegawa, Marialore Sulpizi, Ellen H. G. Backus, Mischa Bonn, and Yuki Nagata
J. Phys. Chem. C 120 (33), 18665–18673 (2016);
doi:10.1021/acs.jpcc.6b06371

At the water–air interface, the hydrogen-bond network of water molecules is interrupted, and accordingly, the structure and dynamics of the interfacial water molecules are altered considerably compared with the bulk. Such interfacial water molecules have been studied by surface-specific vibrational sum-frequency generation (SFG) spectroscopy probing high-frequency O–H stretch and H–O–H bending modes. In contrast, the low-frequency librational mode has been much less studied with SFG. Because this mode is sensitive to the hydrogen-bond connectivity, understanding the librational mode of the interfacial water is crucial for unveiling a microscopic view of the interfacial water. Here, we compute the SFG librational mode spectra at the water–air interface by using molecular dynamics simulation. We show that the modeling of the polarizability has a drastic effect on the simulated librational mode spectra, whereas the spectra are less sensitive to the force field models and the modeling of the dipole moment. The simulated librational spectra display a peak centered at ∼700 cm–1, which is close to the infrared peak frequency of the liquid water librational mode of 670 cm–1. This indicates that the librational mode of the interfacial water at the water–air interface closely resembles that of bulk liquid water.

Molecular Mechanism of Water Evaporation
Yuki Nagata, Kota Usui, Mischa Bonn
Phys. Rev. Lett. 115 (23), 236102 (2015);
doi:10.1103/physrevlett.115.236102

The surface roughness, but not the water molecular orientation varies with temperature at the water–air interface
Yuki Nagata, Taisuke Hasegawa, Ellen H. G. Backus, Kota Usui, Seiji Yoshimune, Tatsuhiko Ohto, Mischa Bonn
Phys. Chem. Chem. Phys. 17 (36), 23559-23564 (2015);
doi:10.1039/c5cp04022a

Ultrafast Vibrational Dynamics of Water Disentangled by Reverse Nonequilibrium Ab Initio Molecular Dynamics Simulations
Yuki Nagata, Seiji Yoshimune, Cho-Shuen Hsieh, Johannes Hunger, Mischa Bonn
Physical Review X 5 (2), 021002 (2015);
doi:10.1103/physrevx.5.021002

Toward ab initio molecular dynamics modeling for sum-frequency generation spectra; an efficient algorithm based on surface-specific velocity-velocity correlation function
Tatsuhiko Ohto, Kota Usui, Taisuke Hasegawa, Mischa Bonn, Yuki Nagata
The Journal of Chemical Physics 143 (12), 124702 (2015);
doi:10.1063/1.4931106

Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution
Kota Usui, Johannes Hunger, Marialore Sulpizi, Tatsuhiko Ohto, Mischa Bonn, and Yuki Nagata
J. Phys. Chem. B 119 (33), 10597–10606 (2015);
doi: 10.1021/acs.jpcb.5b02579

Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)–D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O–D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (OTMAO) atom, due to the O–D···OTMAO hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O–D group rotates (1) after breaking the O–D···OTMAO hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientational slow-down is prominent in the AIMD simulation, simulations based on force field models exhibit much faster dynamics. The simulated angle-resolved radial distribution functions illustrate that the O–D···OTMAO hydrogen-bond has a strong directionality through the sp3 orbital configuration in the AIMD simulation, and this directionality is not properly accounted for in the force field simulation. These results imply that care must be taken when modeling negatively charged oxygen atoms as single point charges; force field models may not adequately describe the hydration configuration and dynamics.

Lipid Carbonyl Groups Terminate the Hydrogen Bond Network of Membrane-Bound Water
Tatsuhiko Ohto, Ellen H. G. Backus, Cho-Shuen Hsieh, Marialore Sulpizi, Mischa Bonn, and Yuki Nagata
J. Phys. Chem. Lett., 6 (22), 4499–4503 (2015);
doi:10.1021/acs.jpclett.5b02141

We present a combined experimental sum-frequency generation (SFG) spectroscopy and ab initio molecular dynamics simulations study to clarify the structure and orientation of water at zwitterionic phosphatidylcholine (PC) lipid and amine N-oxide (AO) surfactant monolayers. Simulated O–H stretch SFG spectra of water show good agreement with the experimental data. The SFG response at the PC interface exhibits positive peaks, whereas both negative and positive bands are present for the similar zwitterionic AO interface. The positive peaks at the water/PC interface are attributed to water interacting with the lipid carbonyl groups, which act as efficient hydrogen bond acceptors. This allows the water hydrogen bond network to reach, with its (up-oriented) O–H groups, into the headgroup of the lipid, a mechanism not available for water underneath the AO surfactant. This highlights the role of the lipid carbonyl group in the interfacial water structure at the membrane interface, namely, stabilizing the water hydrogen bond network.

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