Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO2– and –CO2– Anionic Head Groups by Cold Ion Vibrational Spectroscopy

Abstract

We report the structural evolutions of water networks and solvatochromic response of the CH3NO2– radical anion in the OH and CH stretching regions by analysis of the vibrational spectra displayed by cryogenically cooled CH3NO2–·(H2O)n=1–6 clusters. The OH stretching bands evolve with a surprisingly large discontinuity at n = 6, which features the emergence of an intense, strongly red-shifted band along with a weaker feature that appears in the region assigned to a free OH fundamental. Very similar behavior is displayed by the perdeuterated carboxylate clusters, RCO2–·(H2O)n=5–7 (R = CD3CD2), indicating that this behavior is a general feature in the microhydration of the triatomic anionic domain and not associated with CH oscillators. Electronic structure calculations trace this behavior to the formation of a “book” isomer of the water hexamer that adopts a configuration in which one of the water molecules resides in an acceptor–acceptor–donor (AAD) (A = acceptor, D = donor) H-bonding site. Excitation of the bound OH in the AAD site explores the local network topology best suited to stabilize an incipient –XO2H–OH–(H2O)2 intracluster proton-transfer reaction. These systems thus provide particularly clear examples where the network shape controls the potential energy landscape that governs water network-mediated, intracluster proton transfer. Themore » CH stretching bands of the CH3NO2–·(H2O)n=1–6 clusters also exhibit strong solvatochromic shifts, but in this case, they smoothly blue-shift with increasing hydration with no discontinuity at n = 6. Furthermore, this behavior is analyzed in the context of the solute-ion polarizability response and partial charge transfer to the water networks.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
+ Show Author Affiliations
  1. Yale Univ., New Haven, CT (United States)
  2. Millikin Univ., Decatur, IL (United States)
  3. Univ. of Pittsburgh, PA (United States)
Publication Date:
Research Org.:
Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1864713
Grant/Contract Number:  
SC0021012
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 126; Journal Issue: 16; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Molecular structure; Cluster chemistry; Ions; Molecules

Citation Formats

Mitra, Sayoni, Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Guasco, Timothy L., Choi, Tae Hoon, and Jordan, Kenneth D. Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO2– and –CO2– Anionic Head Groups by Cold Ion Vibrational Spectroscopy. United States: N. p., 2022. Web. doi:10.1021/acs.jpca.2c00721.
Copy to clipboard
Mitra, Sayoni, Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Guasco, Timothy L., Choi, Tae Hoon, & Jordan, Kenneth D. Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO2– and –CO2– Anionic Head Groups by Cold Ion Vibrational Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.2c00721
Copy to clipboard
Mitra, Sayoni, Denton, Joanna K., Kelleher, Patrick J., Johnson, Mark A., Guasco, Timothy L., Choi, Tae Hoon, and Jordan, Kenneth D. Wed . "Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO2– and –CO2– Anionic Head Groups by Cold Ion Vibrational Spectroscopy". United States. https://doi.org/10.1021/acs.jpca.2c00721. https://www.osti.gov/servlets/purl/1864713.
Copy to clipboard
@article{osti_1864713,
title = {Water Network Shape-Dependence of Local Interactions with the Microhydrated –NO2– and –CO2– Anionic Head Groups by Cold Ion Vibrational Spectroscopy},
author = {Mitra, Sayoni and Denton, Joanna K. and Kelleher, Patrick J. and Johnson, Mark A. and Guasco, Timothy L. and Choi, Tae Hoon and Jordan, Kenneth D.},
abstractNote = {We report the structural evolutions of water networks and solvatochromic response of the CH3NO2– radical anion in the OH and CH stretching regions by analysis of the vibrational spectra displayed by cryogenically cooled CH3NO2–·(H2O)n=1–6 clusters. The OH stretching bands evolve with a surprisingly large discontinuity at n = 6, which features the emergence of an intense, strongly red-shifted band along with a weaker feature that appears in the region assigned to a free OH fundamental. Very similar behavior is displayed by the perdeuterated carboxylate clusters, RCO2–·(H2O)n=5–7 (R = CD3CD2), indicating that this behavior is a general feature in the microhydration of the triatomic anionic domain and not associated with CH oscillators. Electronic structure calculations trace this behavior to the formation of a “book” isomer of the water hexamer that adopts a configuration in which one of the water molecules resides in an acceptor–acceptor–donor (AAD) (A = acceptor, D = donor) H-bonding site. Excitation of the bound OH in the AAD site explores the local network topology best suited to stabilize an incipient –XO2H–OH–(H2O)2 intracluster proton-transfer reaction. These systems thus provide particularly clear examples where the network shape controls the potential energy landscape that governs water network-mediated, intracluster proton transfer. The CH stretching bands of the CH3NO2–·(H2O)n=1–6 clusters also exhibit strong solvatochromic shifts, but in this case, they smoothly blue-shift with increasing hydration with no discontinuity at n = 6. Furthermore, this behavior is analyzed in the context of the solute-ion polarizability response and partial charge transfer to the water networks.},
doi = {10.1021/acs.jpca.2c00721},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 16,
volume = 126,
place = {United States},
year = {Wed Apr 13 00:00:00 EDT 2022},
month = {Wed Apr 13 00:00:00 EDT 2022}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpca.2c00721
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

How the Shape of an H-Bonded Network Controls Proton-Coupled Water Activation in HONO Formation
journal, January 2010

Size-Dependent Onset of Nitric Acid Dissociation in Cs + ·(HNO 3 )(H 2 O) n =0–11 Clusters at 20 K
journal, March 2021

  • Mitra, Sayoni; Yang, Nan; McCaslin, Laura M.
  • The Journal of Physical Chemistry Letters, Vol. 12, Issue 13
  • DOI: 10.1021/acs.jpclett.1c00235

Electric Moments of Molecules in Liquids
journal, August 1936

  • Onsager, Lars
  • Journal of the American Chemical Society, Vol. 58, Issue 8
  • DOI: 10.1021/ja01299a050

Potential-dependent water orientation: an in situ spectroscopic study
journal, July 1986

Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface
journal, July 2019

  • Denton, Joanna K.; Kelleher, Patrick J.; Johnson, Mark A.
  • Proceedings of the National Academy of Sciences, Vol. 116, Issue 30
  • DOI: 10.1073/pnas.1818600116

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

Spectroscopic Characterization of Solvent-Mediated Folding in Dicarboxylate Dianions
journal, March 2011

  • Wende, Torsten; Wanko, Marius; Jiang, Ling
  • Angewandte Chemie International Edition, Vol. 50, Issue 16
  • DOI: 10.1002/anie.201006485

Argon predissociation and electron autodetachment spectroscopy of size-selected CH3NO2−⋅Arn clusters
journal, December 2001

  • Weber, J. M.; Robertson, W. H.; Johnson, M. A.
  • The Journal of Chemical Physics, Vol. 115, Issue 23
  • DOI: 10.1063/1.1418251

Microhydration of Nitromethane Anions from Both a Solute and Solvent Perspective
journal, September 2010

  • Marcum, Jesse C.; Weber, J. Mathias
  • The Journal of Physical Chemistry A, Vol. 114, Issue 34
  • DOI: 10.1021/jp103682q

Infrared spectra of the cluster ions H 7 O + 3 ⋅H 2 and H 9 O + 4 ⋅H 2
journal, August 1986

  • Okumura, M.; Yeh, L. I.; Myers, J. D.
  • The Journal of Chemical Physics, Vol. 85, Issue 4
  • DOI: 10.1063/1.451079

Cryogenic Ion Chemistry and Spectroscopy
journal, August 2013

  • Wolk, Arron B.; Leavitt, Christopher M.; Garand, Etienne
  • Accounts of Chemical Research, Vol. 47, Issue 1
  • DOI: 10.1021/ar400125a

A pulsed supersonic entrainment reactor for the rational preparation of cold ionic complexes
journal, January 2000

  • Robertson, W. H.; Kelley, J. A.; Johnson, M. A.
  • Review of Scientific Instruments, Vol. 71, Issue 12
  • DOI: 10.1063/1.1326931

Infrared Signatures of a Water Molecule Attached to Triatomic Domains of Molecular Anions:  Evolution of the H-bonding Configuration with Domain Length
journal, August 2003

  • Robertson, William H.; Price, Erica A.; Weber, J. Mathias
  • The Journal of Physical Chemistry A, Vol. 107, Issue 34
  • DOI: 10.1021/jp030474v

Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Bonded-atom fragments for describing molecular charge densities
journal, January 1977

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Theoretical Study on the Excess Electron Binding Mechanism in the [CH 3 NO 2 ·(H 2 O) n ] − ( n = 1−6) Anion Clusters
journal, September 2010

  • Motegi, Haruki; Takayanagi, Toshiyuki; Tsuneda, Takao
  • The Journal of Physical Chemistry A, Vol. 114, Issue 34
  • DOI: 10.1021/jp1041124

Infrared photodissociation spectroscopy of D 2 -tagged CH 3 CO 2 − (H 2 O) 0−2 anions
journal, April 2020

M OLECULAR A SPECTS OF H ALIDE I ON H YDRATION : The Cluster Approach
journal, October 2003

Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy
journal, May 2012

Large anharmonic effects in the infrared spectra of the symmetrical CH3NO2−⋅(H2O) and CH3CO2−⋅(H2O) complexes
journal, November 2003

  • Myshakin, Evgeniy M.; Jordan, Kenneth D.; Sibert, Edwin L.
  • The Journal of Chemical Physics, Vol. 119, Issue 19
  • DOI: 10.1063/1.1616918

Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex
journal, October 2015

  • Hamm, Peter; Stock, Gerhard
  • The Journal of Chemical Physics, Vol. 143, Issue 13
  • DOI: 10.1063/1.4932189

Vibrational Spectroscopy of the Water–Nitrate Complex in the O–H Stretching Region
journal, April 2014

  • Heine, Nadja; Kratz, Eric G.; Bergmann, Risshu
  • The Journal of Physical Chemistry A, Vol. 118, Issue 37
  • DOI: 10.1021/jp500964j

Two-Dimensional Adiabatic Model for Calculating Progressions Resulting from Stretch–Rock Coupling in Vibrational Spectra of Anion–Water Complexes
journal, July 2021

Disentangling the Complex Vibrational Mechanics of the Protonated Water Trimer by Rational Control of Its Hydrogen Bonds
journal, August 2019

  • Duong, Chinh H.; Yang, Nan; Johnson, Mark A.
  • The Journal of Physical Chemistry A, Vol. 123, Issue 37
  • DOI: 10.1021/acs.jpca.9b05576

Unmasking Rare, Large-Amplitude Motions in D 2 -Tagged I – ·(H 2 O) 2 Isotopomers with Two-Color, Infrared–Infrared Vibrational Predissociation Spectroscopy
journal, June 2018

  • Yang, Nan; Duong, Chinh H.; Kelleher, Patrick J.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 13
  • DOI: 10.1021/acs.jpclett.8b01485

Hydrogen Bond Cooperativity and the Three-Dimensional Structures of Water Nonamers and Decamers
journal, October 2014

  • Pérez, Cristóbal; Zaleski, Daniel P.; Seifert, Nathan A.
  • Angewandte Chemie International Edition, Vol. 53, Issue 52
  • DOI: 10.1002/anie.201407447

Solvation of the Cl - ·H 2 O Complex in CCl 4 Clusters:  The Effect of Solvent-Mediated Charge Redistribution on the Ionic H-Bond
journal, January 2002

  • Robertson, William H.; Weddle, Gary H.; Kelley, Jude A.
  • The Journal of Physical Chemistry A, Vol. 106, Issue 7
  • DOI: 10.1021/jp0137468

Local Mode Approach to OH Stretch Spectra of Benzene–(H 2 O) n Clusters, n = 2–7
journal, August 2015

  • Tabor, Daniel P.; Kusaka, Ryoji; Walsh, Patrick S.
  • The Journal of Physical Chemistry A, Vol. 119, Issue 38
  • DOI: 10.1021/acs.jpca.5b06954

IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively
journal, July 2015

  • Ni, Yicun; Skinner, J. L.
  • The Journal of Chemical Physics, Vol. 143, Issue 1
  • DOI: 10.1063/1.4923462

Spectroscopic Determination of the OH- Solvation Shell in the OH-middle dot(H2O)n Clusters
journal, January 2003

Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n]− clusters
journal, October 2015

  • DeBlase, Andrew F.; Wolke, Conrad T.; Weddle, Gary H.
  • The Journal of Chemical Physics, Vol. 143, Issue 14
  • DOI: 10.1063/1.4931928

Vibrational Spectroscopy of Nitroalkane Chains Using Electron Autodetachment and Ar Predissociation
journal, August 2008

  • Schneider, Holger; Vogelhuber, Kristen M.; Schinle, Florian
  • The Journal of Physical Chemistry A, Vol. 112, Issue 33
  • DOI: 10.1021/jp800124s

On the binding of electrons to nitromethane: Dipole and valence bound anions
journal, September 1996

  • Compton, R. N.; Carman, H. S.; Desfrançois, C.
  • The Journal of Chemical Physics, Vol. 105, Issue 9
  • DOI: 10.1063/1.472993

Ab initio study on radical anions of nitro compounds
journal, February 1992

  • Ramondo, Fabio
  • Canadian Journal of Chemistry, Vol. 70, Issue 2
  • DOI: 10.1139/v92-045

Theoretical and spectroscopic study of asymmetric methyl rotor dynamics in gaseous partially deuterated nitromethanes
journal, April 1993

  • Gorse, Dominique; Cavagnat, Dominique; Pesquer, Michel
  • The Journal of Physical Chemistry, Vol. 97, Issue 17
  • DOI: 10.1021/j100119a005

Vibrational spectra of nitromethanes and the effects of internal rotation
journal, May 1976

Unraveling the Anomalous Solvatochromic Response of the Formate Ion Vibrational Spectrum: An Infrared, Ar-Tagging Study of the HCO 2 ¯ , DCO 2 ¯ , and HCO 2 ¯ ·H 2 O Ions
journal, September 2011

  • Gerardi, Helen K.; DeBlase, Andrew F.; Su, Xiaoge
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 19
  • DOI: 10.1021/jz200937v

Gas-Phase Spectroscopic Signatures of Carboxylate–Li + Contact Ion Pairs: New Benchmarks For Characterizing Ion Pairing in Solution
journal, March 2016

  • Habka, Sana; Brenner, Valérie; Mons, Michel
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 7
  • DOI: 10.1021/acs.jpclett.6b00454

Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state
journal, February 2009

  • Adams, Christopher L.; Schneider, Holger; Ervin, Kent M.
  • The Journal of Chemical Physics, Vol. 130, Issue 7
  • DOI: 10.1063/1.3076892

Laser photoelectron spectroscopy of the formyl anion
journal, March 1986

  • Murray, Kermit K.; Miller, Thomas M.; Leopold, Doreen G.
  • The Journal of Chemical Physics, Vol. 84, Issue 5
  • DOI: 10.1063/1.450371
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: