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Title: Observation of Slow Eigen-Zundel Interconversion in H+(H2O)6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap

Abstract

The formation of isomers when trapping floppy cluster ions in a temperature-controlled ion trap is a generally observed phenomenon. This involves collisional quenching of the ions initially formed at high temperature by buffer gas cooling until their internal energies fall below the barriers in the potential energy surface that separate them. Here we explore the kinetics at play in the case of the two isomers adopted by the H+(H2O)6 cluster ion that differ in the proton accommodation motif. One of these is most like the Eigen cation with a tricoordinated hydronium motif (denoted E), and the other is most like the Zundel ion with the proton equally shared between two water molecules (denoted Z). After initial cooling to about 20 K in the radiofrequency (Paul) trap, the relative populations of these two spectroscopically distinct isomers are abruptly changed through isomer-selective photoexcitation of bands in the OH stretching region with a pulsed (~6 ns) infrared laser while the ions are in the trap. We then monitor the relaxation of the vibrationally excited clusters and reformation of the two cold isomers by recording infrared photodissociation spectra with a second IR laser as a function of delay time from the initial excitation. Themore » latter spectra are obtained after ejecting the trapped ions into a time-of-flight photofragmentation mass spectrometer, thus enabling long (~0.1 s) delay times. Excitation of the Z isomer is observed to display long-lived vibrationally excited states that are collisionally cooled on a ms time scale, some of which quench into the E isomer. These excited E species then display spontaneous interconversion to the Z form on a ~10 ms time scale. Furthermore, these qualitative observations set the stage for a series of experimental measurements that can provide quantitative benchmarks for theoretical simulations of cluster dynamics and the potential energy surfaces that underlie them.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Yale Univ., New Haven, CT (United States)
  2. Univ. of Wisconsin, Madison, WI (United States)
  3. Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Institutes of Health (NIH)
OSTI Identifier:
1963938
Grant/Contract Number:  
SC0021012; SC0021081; 5T32GM008283-32
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Society for Mass Spectrometry
Additional Journal Information:
Journal Volume: 34; Journal Issue: 4; Journal ID: ISSN 1044-0305
Publisher:
American Society for Mass Spectrometry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 47 OTHER INSTRUMENTATION; Protonated water hexamer; isomerization; mass spectrometry; pump-probe; kinetics; collisional cooling; vibrational spectroscopy; Eigen; Zundel; cluster chemistry; cluster ions; ions; lasers; molecular structure

Citation Formats

Khuu, Thien, Rana, Abhijit, Edington, Sean C., Yang, Nan, McCoy, Anne B., and Johnson, Mark A. Observation of Slow Eigen-Zundel Interconversion in H+(H2O)6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap. United States: N. p., 2023. Web. doi:10.1021/jasms.3c00007.
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Khuu, Thien, Rana, Abhijit, Edington, Sean C., Yang, Nan, McCoy, Anne B., & Johnson, Mark A. Observation of Slow Eigen-Zundel Interconversion in H+(H2O)6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap. United States. https://doi.org/10.1021/jasms.3c00007
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Khuu, Thien, Rana, Abhijit, Edington, Sean C., Yang, Nan, McCoy, Anne B., and Johnson, Mark A. Mon . "Observation of Slow Eigen-Zundel Interconversion in H+(H2O)6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap". United States. https://doi.org/10.1021/jasms.3c00007.
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@article{osti_1963938,
title = {Observation of Slow Eigen-Zundel Interconversion in H+(H2O)6 Clusters upon Isomer-Selective Vibrational Excitation and Buffer Gas Cooling in a Cryogenic Ion Trap},
author = {Khuu, Thien and Rana, Abhijit and Edington, Sean C. and Yang, Nan and McCoy, Anne B. and Johnson, Mark A.},
abstractNote = {The formation of isomers when trapping floppy cluster ions in a temperature-controlled ion trap is a generally observed phenomenon. This involves collisional quenching of the ions initially formed at high temperature by buffer gas cooling until their internal energies fall below the barriers in the potential energy surface that separate them. Here we explore the kinetics at play in the case of the two isomers adopted by the H+(H2O)6 cluster ion that differ in the proton accommodation motif. One of these is most like the Eigen cation with a tricoordinated hydronium motif (denoted E), and the other is most like the Zundel ion with the proton equally shared between two water molecules (denoted Z). After initial cooling to about 20 K in the radiofrequency (Paul) trap, the relative populations of these two spectroscopically distinct isomers are abruptly changed through isomer-selective photoexcitation of bands in the OH stretching region with a pulsed (~6 ns) infrared laser while the ions are in the trap. We then monitor the relaxation of the vibrationally excited clusters and reformation of the two cold isomers by recording infrared photodissociation spectra with a second IR laser as a function of delay time from the initial excitation. The latter spectra are obtained after ejecting the trapped ions into a time-of-flight photofragmentation mass spectrometer, thus enabling long (~0.1 s) delay times. Excitation of the Z isomer is observed to display long-lived vibrationally excited states that are collisionally cooled on a ms time scale, some of which quench into the E isomer. These excited E species then display spontaneous interconversion to the Z form on a ~10 ms time scale. Furthermore, these qualitative observations set the stage for a series of experimental measurements that can provide quantitative benchmarks for theoretical simulations of cluster dynamics and the potential energy surfaces that underlie them.},
doi = {10.1021/jasms.3c00007},
journal = {Journal of the American Society for Mass Spectrometry},
number = 4,
volume = 34,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2023},
month = {Mon Mar 27 00:00:00 EDT 2023}
}
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https://doi.org/10.1021/jasms.3c00007
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Works referenced in this record:

Infrared Population Transfer Spectroscopy of Cryo-Cooled Ions: Quantitative Tests of the Effects of Collisional Cooling on the Room Temperature Conformer Populations
journal, February 2018

  • Harrilal, Christopher P.; DeBlase, Andrew F.; Fischer, Joshua L.
  • The Journal of Physical Chemistry A, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpca.7b12751

High-Level VSCF/VCI Calculations Decode the Vibrational Spectrum of the Aqueous Proton
journal, July 2019

  • Yu, Qi; Carpenter, William B.; Lewis, Nicholas H. C.
  • The Journal of Physical Chemistry B, Vol. 123, Issue 33
  • DOI: 10.1021/acs.jpcb.9b05723

Gas phase vibrational spectroscopy of the protonated water pentamer: the role of isomers and nuclear quantum effects
journal, January 2016

  • Fagiani, Matias R.; Knorke, Harald; Esser, Tim K.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 38
  • DOI: 10.1039/C6CP05217G

Controlled synthesis and analysis of He–H + 3 in a 3.7 K ion trap
journal, May 2014

Collisional state-changing of OH− rotations by interaction with Rb atoms in cold traps
journal, November 2015

Hydration-induced protomer switching in p-aminobenzoic acid studied by cold double ion trap infrared spectroscopy
journal, January 2023

  • Akasaka, Kyota; Hirata, Keisuke; Haddad, Fuad
  • Physical Chemistry Chemical Physics, Vol. 25, Issue 6
  • DOI: 10.1039/D2CP04497H

Direct measurement of the energy thresholds to conformational isomerization. II. 3-indole-propionic acid and its water-containing complex
journal, June 2005

  • Clarkson, Jasper R.; Baquero, Esteban; Zwier, Timothy S.
  • The Journal of Chemical Physics, Vol. 122, Issue 21
  • DOI: 10.1063/1.1924455

Ionic Liquid Clusters Generated from Electrospray Thrusters: Cold Ion Spectroscopic Signatures of Size-Dependent Acid–Base Interactions
journal, December 2020

  • Zeng, Helen J.; Khuu, Thien; Chambreau, Steven D.
  • The Journal of Physical Chemistry A, Vol. 124, Issue 50
  • DOI: 10.1021/acs.jpca.0c07595

Laser-Initiated Shuttling of a Water Molecule Between H-Bonding Sites
journal, March 2005

The Role of Electrical Anharmonicity in the Association Band in the Water Spectrum
journal, April 2014

  • McCoy, Anne B.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 28
  • DOI: 10.1021/jp501647e

Direct Measurement of Energy Thresholds to Conformational Isomerization in Tryptamine
journal, February 2004

Conformational Dynamics in a Dipeptide After Single-Mode Vibrational Excitation
journal, June 2002

Investigations of Protonated and Deprotonated Water Clusters Using a Low-Temperature 22-Pole Ion Trap
journal, May 2003

  • Wang, Y. -S.; Tsai, C. -H.; Lee, Y. T.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 21
  • DOI: 10.1021/jp022156m

Mapping the temperature-dependent and network site-specific onset of spectral diffusion at the surface of a water cluster cage
journal, October 2020

  • Yang, Nan; Edington, Sean C.; Choi, Tae Hoon
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 42
  • DOI: 10.1073/pnas.2017150117

Micromotion-Induced Limit to Atom-Ion Sympathetic Cooling in Paul Traps
journal, December 2012

Thermodynamics of Water Dimer Dissociation in the Primary Hydration Shell of the Iodide Ion with Temperature-Dependent Vibrational Predissociation Spectroscopy
journal, February 2015

  • Wolke, Conrad T.; Menges, Fabian S.; Tötsch, Niklas
  • The Journal of Physical Chemistry A, Vol. 119, Issue 10
  • DOI: 10.1021/jp510250n

Benchmark Electronic Structure Calculations for H 3 O + (H 2 O) n , n = 0–5, Clusters and Tests of an Existing 1,2,3-Body Potential Energy Surface with a New 4-Body Correction
journal, August 2018

  • Heindel, Joseph P.; Yu, Qi; Bowman, Joel M.
  • Journal of Chemical Theory and Computation, Vol. 14, Issue 9
  • DOI: 10.1021/acs.jctc.8b00598

Infrared Spectra of H + (H 2 O) 5 - 8 Clusters:  Evidence for Symmetric Proton Hydration
journal, February 2000

  • Jiang, Jyh-Chiang; Wang, Yi-Sheng; Chang, Hai-Chou
  • Journal of the American Chemical Society, Vol. 122, Issue 7
  • DOI: 10.1021/ja990033i

Collisional relaxation of photoexcited bromobenzene ions by various neutral partners
journal, May 1987

  • Ahmed, M. Saber; Dunbar, Robert C.
  • Journal of the American Chemical Society, Vol. 109, Issue 11
  • DOI: 10.1021/ja00245a005

The dynamics of conformational isomerization in flexible biomolecules. I. Hole-filling spectroscopy of N-acetyl tryptophan methyl amide and N-acetyl tryptophan amide
journal, January 2004

  • Dian, Brian C.; Longarte, Asier; Winter, Paul R.
  • The Journal of Chemical Physics, Vol. 120, Issue 1
  • DOI: 10.1063/1.1626540

Isomer-Selective Detection of Hydrogen-Bond Vibrations in the Protonated Water Hexamer
journal, May 2013

  • Heine, Nadja; Fagiani, Matias R.; Rossi, Mariana
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja401359t

Reexamination of the Quenching of NO+ Vibrations by O2(a 1Δg)
journal, June 2010

  • Eyet, Nicole; Viggiano, A. A.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 28
  • DOI: 10.1021/jp1042987

Origin of the diffuse vibrational signature of a cyclic intramolecular proton bond: Anharmonic analysis of protonated 1,8-disubstituted naphthalene ions
journal, July 2013

  • DeBlase, Andrew F.; Bloom, Steven; Lectka, Thomas
  • The Journal of Chemical Physics, Vol. 139, Issue 2
  • DOI: 10.1063/1.4810878

Vibrational Signatures of HNO3 Acidity When Complexed with Microhydrated Alkali Metal Ions, M+·(HNO3)(H2O)n=5 (M = Li, K, Na, Rb, Cs), at 20 K
journal, March 2022

  • Mitra, Sayoni; Khuu, Thien; Choi, Tae Hoon
  • The Journal of Physical Chemistry A, Vol. 126, Issue 10
  • DOI: 10.1021/acs.jpca.1c10352

Preparation and Characterization of the Halogen-Bonding Motif in the Isolated Cl–·IOH Complex with Cryogenic Ion Vibrational Spectroscopy
journal, March 2022

  • Stropoli, Santino J.; Khuu, Thien; Messinger, Joseph P.
  • The Journal of Physical Chemistry Letters, Vol. 13, Issue 12
  • DOI: 10.1021/acs.jpclett.2c00218

Hidden role of intermolecular proton transfer in the anomalously diffuse vibrational spectrum of a trapped hydronium ion
journal, May 2017

  • Craig, Stephanie M.; Menges, Fabian S.; Duong, Chinh H.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 24
  • DOI: 10.1073/pnas.1705089114
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