Theoretical Vibrational Spectroscopy of Aqueous Solutions

• Applicant: Professor Dr. Dominik Marx
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2011 to 2025
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 193464650

• Final Report Year: 2025

Final Report Abstract

Vibrational spectroscopy is a powerful approach employed since long to investigate the structure and dynamics of aqueous systems. Since decades, high-frequency intramolecular modes have been used as specific reporter modes in the mid-infrared frequency range, whereas not long ago it has been found that a wealth of complementary information can be gained by probing low-frequency inter-molecular motion in the far-infrared regime. The latter modes couple most directly into the hydrogen-bond network dynamics and are thus reporters for the intricate network dynamics in aqueous environments. We extended and generalized methods to quantitatively compute and fully assign far-infrared spectra and applied them to disclose the structural dynamics of aqueous solutions including bulk, nanoconfined and supercritical water as well as finite clusters as seen by far-infrared spectroscopy.

Publications

• Terahertz Spectra of Microsolvated Ions: Do They Reveal Bulk Solvation Properties?. The Journal of Physical Chemistry Letters, 10(3), 393-398.
  Gupta, Prashant Kumar; Schienbein, Philipp; Daru, Janos & Marx, Dominik
  
• Probing Local Electrostatics of Glycine in Aqueous Solution by THz Spectroscopy. Angewandte Chemie International Edition, 60(7), 3768-3772.
  Sebastiani, Federico; Ma, Chun Yu; Funke, Sarah; Bäumer, Alexander; Decka, Dominique; Hoberg, Claudius; Esser, Alexander; Forbert, Harald; Schwaab, Gerhard; Marx, Dominik & Havenith, Martina
  
• Supercritical Water is not Hydrogen Bonded. Angewandte Chemie International Edition, 59(42), 18578-18585.
  Schienbein, Philipp & Marx, Dominik
  
• Dielectric relaxation of water: assessing the impact of localized modes, translational diffusion, and collective dynamics. Physical Chemistry Chemical Physics, 23(37), 20875-20882.
  Hölzl, Christoph; Forbert, Harald & Marx, Dominik
  
• Nanoconfinement effects on water in narrow graphene-based slit pores as revealed by THz spectroscopy. Physical Chemistry Chemical Physics, 24(40), 24734-24747.
  Ruiz-Barragan, Sergi; Sebastiani, Federico; Schienbein, Philipp; Abraham, Jijo; Schwaab, Gerhard; Nair, Rahul R.; Havenith, Martina & Marx, Dominik
  
• Deciphering the Properties of Nanoconfined Aqueous Solutions by Vibrational Sum Frequency Generation Spectroscopy. The Journal of Physical Chemistry Letters, 14(5), 1208-1213.
  Das, Banshi; Ruiz-Barragan, Sergi & Marx, Dominik
  
• Ion Effects on Terahertz Spectra of Microsolvated Clusters. The Journal of Physical Chemistry Letters, 15(50), 12387-12392.
  Jindal, Aman; Schienbein, Philipp; Gupta, Prashant Kumar & Marx, Dominik
  
• Nuclear Quantum Effects Have a Significant Impact on UV/Vis Absorption Spectra of Chromophores in Water. Angewandte Chemie International Edition, 64(3).
  Tsuru, Shota; Sharma, Bikramjit; Hättig, Christof & Marx, Dominik
  
• Solvation Properties of Neutral Gold Species in Supercritical Water Studied By THz Spectroscopy. Angewandte Chemie International Edition, 63(28).
  Noetzel, Jan; Schienbein, Philipp; Forbert, Harald & Marx, Dominik
  
• Random encounters dominate water-water interactions at supercritical conditions. Science Advances, 11(11).
  Mauelshagen, Katja; Schienbein, Philipp; Kolling, Inga; Schwaab, Gerhard; Marx, Dominik & Havenith, Martina