Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K

Mitra, Sayoni; Yang, Nan; McCaslin, Laura M.; Gerber, R. Benny; Johnson, Mark A.

doi:10.1021/acs.jpclett.1c00235

Title: Size-Dependent Onset of Nitric Acid Dissociation in Cs⁺·(HNO₃)(H₂O)_n=0–11 Clusters at 20 K

Abstract

We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs⁺∙(HNO₃)(H₂O)_n=0-11 clusters at 20 K. Dramatic spectral changes are observed in the range n=7-9 that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n=10, which exhibits much simpler vibrational band patterns consistent with those expected for a tri-coordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO₃^– anion that is directly complexed to the Cs⁺ cation. Theoretical analysis of the n=10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs⁺ and H₃O⁺ cations flank the NO₃^– anion in a microhydrated salt bridge. In conclusion, this charge separation motif is evidently assisted by the electrostatic stabilization of the product NO₃^–/H₃O⁺ ion pair by the proximal metal ion.

Authors:

^[1];

^[2];

^[3];

^[1]

Yale Univ., New Haven, CT (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
The Hebrew Univ., Jerusalem (Israel); Univ. of California, Irvine, CA (United States)

Publication Date:: Mon Mar 29 00:00:00 EDT 2021

Research Org.:: Yale Univ., New Haven, CT (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1773044

Grant/Contract Number:: SC0021012; FG02-06ER15800; NA0003525

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 12; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Acid dissociation; Mass spectrometry; Infrared spectroscopy

Citation Formats


                    Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, and Johnson, Mark A. Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K.  United States: N. p., 2021. 
Web.  doi:10.1021/acs.jpclett.1c00235.

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                    Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, & Johnson, Mark A. Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K.  United States.  https://doi.org/10.1021/acs.jpclett.1c00235

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                    Mitra, Sayoni, Yang, Nan, McCaslin, Laura M., Gerber, R. Benny, and Johnson, Mark A. Mon .  
"Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K".  United States.  https://doi.org/10.1021/acs.jpclett.1c00235.  https://www.osti.gov/servlets/purl/1773044.

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@article{osti_1773044,

  title        = {Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K},

  author       = {Mitra, Sayoni and Yang, Nan and McCaslin, Laura M. and Gerber, R. Benny and Johnson, Mark A.},

  abstractNote = {We report the water-mediated charge separation of nitric acid upon incorporation into size-selected Cs+∙(HNO3)(H2O)n=0-11 clusters at 20 K. Dramatic spectral changes are observed in the range n=7-9 that are traced to the formation of many isomeric structures associated with intermediate transfer of the acidic proton to the water network. This transfer is complete by n=10, which exhibits much simpler vibrational band patterns consistent with those expected for a tri-coordinated hydronium ion (the Eigen motif) along with the NO stretching bands predicted for a hydrated NO3– anion that is directly complexed to the Cs+ cation. Theoretical analysis of the n=10 spectrum indicates that the dissociated ions adopt a solvent-separated ion-pair configuration such that the Cs+ and H3O+ cations flank the NO3– anion in a microhydrated salt bridge. In conclusion, this charge separation motif is evidently assisted by the electrostatic stabilization of the product NO3–/H3O+ ion pair by the proximal metal ion.},

  doi          = {10.1021/acs.jpclett.1c00235},

  journal      = {Journal of Physical Chemistry Letters},

  number       = ,

  volume       = 12,

  place        = {United States},

  year         = {Mon Mar 29 00:00:00 EDT 2021},

  month        = {Mon Mar 29 00:00:00 EDT 2021}

}

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Title: Size-Dependent Onset of Nitric Acid Dissociation in Cs+·(HNO3)(H2O)n=0–11 Clusters at 20 K

Abstract

Citation Formats

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

Ionization of Nitric Acid on Crystalline Ice: The Role of Defects and Collective Proton Movement journal, May 2013

Ions at the Air/Water Interface journal, June 2002

Spectroscopic Study of HNO 3 Dissociation on Ice journal, November 2012

Acid Ionization of HBr in a Small Water Cluster journal, January 1999

Glancing-angle Raman study of nitrate and nitric acid at the air–aqueous interface journal, January 2012

At the Water's Edge: Nitric Acid as a Weak Acid journal, October 2007

Elucidating the mechanism of selective ion adsorption to the liquid water surface journal, January 2012

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

Microhydration of Cs+ ion: A density functional theory study on Cs+–(H2O)n clusters (n=1–10) journal, July 2007

Vibrational Spectra of Isotopic Nitric Acids journal, January 1965

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Nonlinear Vibrational Spectroscopic Studies of the Adsorption and Speciation of Nitric Acid at the Vapor/Acid Solution Interface journal, May 2007

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Interaction of HNO 3 with water-ice surfaces at temperatures of the free troposphere journal, June 1997

Hydrated Alkali-Metal Cations: Infrared Spectroscopy and ab Initio Calculations of M + (H 2 O) x =2−5 Ar cluster ions for M = Li, Na, K, and Cs journal, November 2008

Toward a Unified Picture of the Water Self-Ions at the Air–Water Interface: A Density Functional Theory Perspective journal, May 2014

Nitric Acid−Water Interaction Probed via Isolation in Carbon Tetrachloride † journal, June 2007

Infrared spectra of the solvated hydronium ion: Vibrational predissociation spectroscopy of mass-selected H3O+.cntdot.(H2O)n.cntdot.(H2)m journal, May 1990

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Title: Size-Dependent Onset of Nitric Acid Dissociation in Cs⁺·(HNO₃)(H₂O)_n=0–11 Clusters at 20 K

Experiments and Simulations of Ion-Enhanced Interfacial Chemistry on Aqueous NaCl Aerosols
journal, April 2000

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

Ionization of Nitric Acid on Crystalline Ice: The Role of Defects and Collective Proton Movement
journal, May 2013

Ions at the Air/Water Interface
journal, June 2002

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journal, November 2012

Acid Ionization of HBr in a Small Water Cluster
journal, January 1999

Glancing-angle Raman study of nitrate and nitric acid at the air–aqueous interface
journal, January 2012

At the Water's Edge: Nitric Acid as a Weak Acid
journal, October 2007

Elucidating the mechanism of selective ion adsorption to the liquid water surface
journal, January 2012

Deconstructing water’s diffuse OH stretching vibrational spectrum with cold clusters
journal, April 2019

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

Microhydration of Cs+ ion: A density functional theory study on Cs+–(H2O)n clusters (n=1–10)
journal, July 2007

Vibrational Spectra of Isotopic Nitric Acids
journal, January 1965

The Nitric Acid−Water Complex: Microwave Spectrum, Structure, and Tunneling
journal, February 1998

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

Tag-Free and Isotopomer-Selective Vibrational Spectroscopy of the Cryogenically Cooled H ₉ O ₄ ⁺ Cation with Two-Color, IR–IR Double-Resonance Photoexcitation: Isolating the Spectral Signature of a Single OH Group in the Hydronium Ion Core
journal, October 2018

Entropic Effects on Hydrated Alkali-Metal Cations: Infrared Spectroscopy and ab Initio Calculations of M ⁺ (H ₂ O) _{x =2−5} Cluster Ions for M = Li, Na, K, and Cs
journal, November 2008

An atmospherically relevant acid: HNO3
journal, May 2011

Does Nitric Acid Dissociate at the Aqueous Solution Surface?
journal, September 2011

Cryogenic Ion Chemistry and Spectroscopy
journal, August 2013

Aggregation-Induced Dissociation of HCl(H2O)4 Below 1 K: The Smallest Droplet of Acid
journal, June 2009

The impact of cloud particle gravitational settling on soluble trace gas distributions
journal, January 1998

Theoretical study of the protolytic dissociation of HCl in water clusters
journal, July 2001

Depth-Dependent Dissociation of Nitric Acid at an Aqueous Surface: Car−Parrinello Molecular Dynamics
journal, February 2009

Nonlinear Vibrational Spectroscopic Studies of the Adsorption and Speciation of Nitric Acid at the Vapor/Acid Solution Interface
journal, May 2007

Simulation and Theory of Ions at Atmospherically Relevant Aqueous Liquid-Air Interfaces
journal, April 2013

Isomer-specific cryogenic ion vibrational spectroscopy of the D ₂ tagged Cs ⁺ (HNO ₃ )(H ₂ O) _n=0–2 complexes: ion-driven enhancement of the acidic H-bond to water
journal, January 2020

Interaction of HNO ₃ with water-ice surfaces at temperatures of the free troposphere
journal, June 1997

Hydrated Alkali-Metal Cations: Infrared Spectroscopy and ab Initio Calculations of M ⁺ (H ₂ O) _{x =2−5} Ar cluster ions for M = Li, Na, K, and Cs
journal, November 2008

Toward a Unified Picture of the Water Self-Ions at the Air–Water Interface: A Density Functional Theory Perspective
journal, May 2014

Nitric Acid−Water Interaction Probed via Isolation in Carbon Tetrachloride ^†
journal, June 2007

Infrared spectra of the solvated hydronium ion: Vibrational predissociation spectroscopy of mass-selected H3O+.cntdot.(H2O)n.cntdot.(H2)m
journal, May 1990

Uptake of HNO ₃ on ice under upper tropospheric conditions
journal, June 1997

The Bending Mode of Water: A Powerful Probe for Hydrogen Bond Structure of Aqueous Systems
journal, September 2020

Caught in the Act of Dissolution
journal, October 2002

Uptake of HNO₃ to deliquescent sea-salt particles: a study using the short-lived radioactive isotope tracer ¹³N
journal, January 2002

C HEMISTRY AND M ICROPHYSICS OF P OLAR S TRATOSPHERIC C LOUDS AND C IRRUS C LOUDS
journal, October 2000

Uptake of Nitric Acid on Ice at Tropospheric Temperatures: Implications for Cirrus Clouds ^†
journal, October 2002

Spectroscopic snapshots of the proton-transfer mechanism in water
journal, December 2016

Acid Dissolution by Aqueous Surfaces and Ice: Insights from a Study of Water Cluster Ions ^†
journal, June 2001

Laboratory Studies of Potential Mechanisms of Renoxification of Tropospheric Nitric Acid
journal, February 2003

Quantum chemical insights into the dissociation of nitric acid on the surface of aqueous electrolytes
journal, May 2012

Infrared Spectroscopic Evidence for Protonated Water Clusters Forming Nanoscale Cages
journal, May 2004

Snapshots of Proton Accommodation at a Microscopic Water Surface: Understanding the Vibrational Spectral Signatures of the Charge Defect in Cryogenically Cooled H ⁺ (H ₂ O) _{n =2–28} Clusters
journal, July 2015