Large-scale and small-scale diffusive and dielectric aspects of proton motion

Principal Investigator: Prof. Dr. Roland Netz (FU)

To understand proton transfer on the molecular level, IR absorption spectra will be derived from ab initio simulations of excess protons that move via water molecules between specific donor and acceptor pairs and decomposed into contributions from normal modes, proton transition paths and two-state proton switching. IR line shapes will be interpreted in terms of frequency-dependent friction due to the environment of a vibrating chemical bond. Interaction energies between protons and other ions in cylindrical and planar aqueous cavities will be derived from force-field as well as from ab initio molecular-dynamics simulations.

Publications

2021 - 2024

Brünig, F.N., Daldrop, J.O. and Netz, R.R. (2022). Pair-Reaction Dynamics in Water: Competition of Memory, Potential Shape, and Inertial Effects. J Phys Chem B. doi: 10.1021/acs.jpcb.2c05923.

Brünig, F.N., Geburtig, O., von Canal, A., Kappler, J., and Netz, R.R. (2022). Time-dependent friction effects on vibrational infrared frequencies and line shapes of liquid water. J Phys Chem B, 126, 7: 1579–1589. doi: 10.1021/acs.jpcb.1c09481.

Brünig, F.N., Hillmann, P., Kim, W.K., Daldrop, J.O. and Netz, R.R. (2022). Proton-transfer spectroscopy beyond the normal-mode scenario. J Chem Phys, 157, 17: 174116. doi: 10.1063/5.0116686.

Brünig, F.N., Netz, R.R. and Kappler, J. (2022). Barrier-crossing times for different non-Markovian friction in well and barrier: A numerical study. Phys Rev E, 106, 4: 044133. doi: 10.1103/PhysRevE.106.044133.

Brünig, F.N., Rammler, M., Adams, E.M., Havenith, M. and Netz, R.R. (2022). Spectral signatures of excess-proton waiting and transfer-path dynamics in aqueous hydrochloric acid solutions. Nat Commun, 13, 1: 4210. doi: 10.1038/s41467-022-31700-x.

Dalton, B.A. and Netz, R.R. (2024). pH Modulates Friction Memory Effects in Protein Folding. Physical Review Letters, 133, 18: doi:10.1103/PhysRevLett.133.188401.

Fellows, A.P., Duque, A.D., Balos, V., Lehmann, L., Netz, R.R., Wolf, M. and Thamer, M. (2024). How Thick is the Air-Water Interface? - A Direct Experimental Measurement of the Decay Length of the Interfacial Structural Anisotropy. Langmuir, 40, 35: 18760-18772. doi: 10.1021/acs.langmuir.4c02571.

Gonella, G., Backus, E.H.G., Nagata, Y., Bonthuis, D.J., Loche, P., Schlaich, A., Netz, R.R., Kühnle, A., McCrum, I.T., Koper, M.T.M., Wolf, M., Winter, B., Meijer, G., Campen, R.K., and Bonn, M. (2021). Water at charged interfaces. Nat Rev Chem, 5: 466–485. doi: 10.1038/s41570-021-00293-2.

Liese, S., Schlaich, A. and Netz, R.R. (2022). Dielectric constant of aqueous solutions of proteins and organic polymers from molecular dynamics simulations. J Chem Phys, 156, 22: 224902. doi: 10.1063/5.0089397.

Scalfi, L., Lehmann, L., Dos Santos, A.P., Becker, M.R. and Netz, R.R. (2024). Propensity of hydroxide and hydronium ions for the air-water and graphene-water interfaces from ab initio and force field simulations. J Chem Phys, 161, 14: doi:10.1063/5.0226966.

Yang, Y., Stensitzki, T., Sauthof, L., Schmidt, A., Piwowarski, P., Velazquez Escobar, F., Michael, N., Nguyen, A.D., Szczepek, M., Brünig, F. N., Netz, R.R., Mroginski, M.A., Adam, S., Bartl, F., Schapiro, I., Hildebrandt, P., Scheerer, P., and Heyne, K. (2022). Ultrafast proton-coupled isomerization in the phototransformation of phytochrome. Nat Chem. doi: 10.1038/s41557-022-00944-x.

2017 - 2020

Balos, V., Imoto, S., Netz, R.R., Bonn, M., Bonthuis, D.J., Nagata, Y., and Hunger, J. (2020). Macroscopic conductivity of aqueous electrolyte solutions scales with ultrafast microscopic ion motions. Nat Commun 11, 1611. doi: 10.1038/s41467-020-15450-2.

Daldrop, J.O., Kappler, J., Brünig, F. N., and Netz, R.R. (2018). Butane dihedral angle dynamics in water is dominated by internal friction. Proc Natl Acad Sci USA 115, 5169-5174; doi: 10.1073/pnas.1722327115

Daldrop, J.O., Saita, M., Heyden, M., Lorenz-Fonfria, V. A., Heberle. J., and Netz, R.R. (2018). Orientation of non-spherical protonated water clusters revealed by infrared absorption dichroism. Nature Communications 9, 311; doi: 10.1038/s41467-017-02669-9

Friedrich, D., Brünig, F.N., Nieuwkoop, A.J., Netz, R.R., Hegemann, P. and Oschkinat, H. (2020). Collective exchange processes reveal an active site proton cage in bacteriorhodopsin. Commun. Biol. 3, doi: 10.1038/s42003-019-0733-7

Gravelle, S., Netz, R.R., and Bocquet, L. (2019). Adsorption Kinetics in Open Nanopores as a Source of Low-Frequency Noise. Nano Lett. 19, 7265–7272; doi: 10.1021/acs.nanolett.9b02858

Loche, P., Ayaz, C.,Schlaich, A., Uematsu, Y., and Netz, R.R. (2019). Giant Axial Dielectric Response in Water-Filled Nanotubes and Effective Electrostatic Ion−Ion Interactions from a Tensorial Dielectric Model. J. Phys. Chem. B 123,50, 10850-10857, doi: 10.1021/acs.jpcb.9b09269

Loche, P., Wolde-Kidan, A., Schlaich, A., Bonthuis, D. J., and Netz, R.R. (2019). Comment on “Hydrophobic Surface Enhances Electrostatic Interaction in Water” Phys. Rev. Lett. 123, 049601, doi: 10.1103/PhysRevLett.123.049601

Mamatkulov, S. I., Allolio, C., Netz, R.R., and Bonthuis, D. J. (2017). Orientation-Induced Adsorption of Hydrated Protons at the Air–Water Interface. Angew. Chem. - Int. Edt. 56, 15846–15851; doi: 10.1002/anie.201707391

Mamatkulov, S. I., Rinne, K. F., Buchner, R., Netz, R.R., and Bonthuis, D. J. (2018). Water-separated ion pairs cause the slow dielectric mode of magnesium sulfate solutions. J Chem Phys 148, 222812; doi: 10.1063/1.5000385

Wolde-Kidan, A., Pham, Q. D., Schlaich, A., Loche, P., Sparr, E., Netz, R.R., and Schneck, E. (2019). Influence of polar co-solutes and salt on the hydration of lipid membranes. Phys. Chem. Chem. Phys., 21, 16989–17000; doi: 10.1039/C9CP01953G

2013 - 2016

Bonthuis, D.J., Mamatkulov, S., and Netz, R.R. (2016). Optimization of classical nonpolarizable force fields for OH^- and H₃O⁺. Journal of Chemical Physics 144, 104503

Bonthuis, D.J., and Netz, R.R. (2013). Beyond the Continuum: How Molecular Solvent Structure Affects Electrostatics and Hydrodynamics at Solid-Electrolyte Interfaces. Journal of Physical Chemistry B 117, 11397-11413.

Bonthuis, D.J., Uematsu, Y., and Netz, R.R. (2016). Interfacial layer effects on surface capacitances and electro-osmosis in electrolytes. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 374, 20150033.

Daldrop, J.O., Kim, W.K., and Netz, R.R. (2016). Transition paths are hot. Europhys. Lett. 113, 18004.

Gekle, S., and Netz, R.R. (2014). Nanometer-Resolved Radio-Frequency Absorption and Heating in Biomembrane Hydration Layers. Journal of Physical Chemistry B 118, 4963-4969.

Kim, W.K., and Netz, R.R. (2015). Barrier-induced dielectric counterion relaxation at super-low frequencies in salt-free polyelectrolyte solutions. European Physical Journal E 38, 120.

Kim, W.K., and Netz, R.R. (2015). The mean shape of transition and first-passage paths. Journal of Chemical Physics 143, 224108.

Mamatkulov, S., Fyta, M., and Netz, R.R. (2013). Force fields for divalent cations based on single-ion and ion-pair properties. Journal of Chemical Physics 138, 024505.

Rinne, K.F., Gekle, S., and Netz, R.R. (2014). Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions. Journal of Chemical Physics 141, 214502.

Rinne, K.F., Gekle, S., and Netz, R.R. (2014). Ion-Specific Solvation Water Dynamics: Single Water versus Collective Water Effects. Journal of Physical Chemistry A 118, 11667-11677.

Rinne, K.F., Schulz, J.C.F., and Netz, R.R. (2015). Impact of secondary structure and hydration water on the dielectric spectrum of poly-alanine and possible relation to the debate on slaved versus slaving water. Journal of Chemical Physics 142, 215104.

Schlaich, A., Knapp, E.W., and Netz, R.R. (2016). Water Dielectric Effects in Planar Confinement. Phys Rev Lett 117, 048001. [Link to news section.]

Schwierz, N., Horinek, D., and Netz, R.R. (2015). Specific Ion Binding to Carboxylic Surface Groups and the pH Dependence of the Hofmeister Series. Langmuir 31, 215-225.

Schwierz, N., Horinek, D., Sivan, U.,and Netz, R.R. (2016). Reversed Hofmeister series - The rule rather than the exception. Current Opinion in Colloid & Interface Science 23, 10-18.

Sedlmeier, F., Shadkhoo, S., Bruinsma, R., and Netz, R.R. (2016). Charge/mass dynamic structure factors of water and applications to dielectric friction and electroacoustic conversion. Journal of Chemical Physics 140, 054512.

von Hansen, Y., Gekle, S., and Netz, R.R. (2013). Anomalous Anisotropic Diffusion Dynamics of Hydration Water at Lipid Membranes. Physical Review Letters 111, 118103.