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State-resolved infrared spectrum of the protonated water dimer: revisiting the characteristic proton transfer doublet peak

Larsson, Henrik R. and Schröder, Markus and Beckmann, Richard and Brieuc, Fabien and Schran, Christoph and Marx, Dominik and Vendrell, Oriol (2022) State-resolved infrared spectrum of the protonated water dimer: revisiting the characteristic proton transfer doublet peak. Chemical Science, 13 (37). pp. 11119-11125. ISSN 2041-6520. doi:10.1039/d2sc03189b.

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The infrared (IR) spectra of protonated water clusters encode precise information on the dynamics and structure of the hydrated proton. However, the strong anharmonic coupling and quantum effects of these elusive species remain puzzling up to the present day. Here, we report unequivocal evidence that the interplay between the proton transfer and the water wagging motions in the protonated water dimer (Zundel ion) giving rise to the characteristic doublet peak is both more complex and more sensitive to subtle energetic changes than previously thought. In particular, hitherto overlooked low-intensity satellite peaks in the experimental spectrum are now unveiled and mechanistically assigned. Our findings rely on the comparison of IR spectra obtained using two highly accurate potential energy surfaces in conjunction with highly accurate state-resolved quantum simulations. We demonstrate that these high-accuracy simulations are important for providing definite assignments of the complex IR signals of fluxional molecules.

Item Type:Article
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URLURL TypeDescription
Larsson, Henrik R.0000-0002-9417-1518
Schröder, Markus0000-0002-8032-9791
Schran, Christoph0000-0003-4595-5073
Vendrell, Oriol0000-0003-4629-414X
Additional Information:The authors thank Professor Joel Bowman for having made their potential energy surface available. HRL acknowledges support from the University of California Merced start-up funding during the last part of this work. HRL acknowledges support from a postdoctoral fellowship from the German Research Foundation (DFG) via grant LA 4442/1-1 during the first part of this work. HRL acknowledges computational time both on the Pinnacles cluster at UC Merced (supported by NSF OAC-2019144) and at the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. The Bochum work has been funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC 2033 – 390677874 – RESOLV as well as by the individual DFG grant MA 1547/19 to DM and supported by the “Center for Solvation Science ZEMOS” funded by the German Federal Ministry of Education and Research and by the Ministry of Culture and Research of North Rhine-Westphalia. RB acknowledges funding from the Studienstiftung des deutschen Volkes and CS acknowledges partial financial support from the Alexander von Humboldt-Stiftung. MS and OV thank the High Performance Computing Center in Stuttgart (HLRS) under the grant number HDQM_MCT as well as the bwHPC project of the state of Baden-Württemberg under grant number bw18K011 for providing computational resources.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Studienstiftung des Deutschen VolkesUNSPECIFIED
Alexander von Humboldt FoundationUNSPECIFIED
Deutsche Forschungsgemeinschaft (DFG)LA 4442/1-1
Deutsche Forschungsgemeinschaft (DFG)390677874
Deutsche Forschungsgemeinschaft (DFG)MA 1547/19
Resnick Sustainability InstituteUNSPECIFIED
University of California, MercedUNSPECIFIED
Issue or Number:37
Record Number:CaltechAUTHORS:20220916-665970000
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:117027
Deposited By: Olivia Warschaw
Deposited On:25 Oct 2022 23:07
Last Modified:25 Oct 2022 23:07

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