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

Mitra, Sayoni; Denton, Joanna K.; Kelleher, Patrick J.; Johnson, Mark A.; Guasco, Timothy L.; Choi, Tae Hoon; Jordan, Kenneth D.

doi:10.1021/acs.jpca.2c00721

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

Journal Article · Wed Apr 13 00:00:00 EDT 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.2c00721· OSTI ID:1864713

^[1]; Denton, Joanna K. ^[1];

^[1];

^[2];

^[3];

^[3]

Yale Univ., New Haven, CT (United States)
Millikin Univ., Decatur, IL (United States)
Univ. of Pittsburgh, PA (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021012

OSTI ID:: 1864713

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 126, Issue 16; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

How the Shape of an H-Bonded Network Controls Proton-Coupled Water Activation in HONO Formation Relph, R. A.; Guasco, T. L.; Elliott, B. M. Science, Vol. 327, Issue 5963 https://doi.org/10.1126/science.1177118	journal	January 2010
Size-Dependent Onset of Nitric Acid Dissociation in Cs ⁺ ·(HNO ₃ )(H ₂ O) _{n =0–11} Clusters at 20 K Mitra, Sayoni; Yang, Nan; McCaslin, Laura M. The Journal of Physical Chemistry Letters, Vol. 12, Issue 13 https://doi.org/10.1021/acs.jpclett.1c00235	journal	March 2021
Electric Moments of Molecules in Liquids Onsager, Lars Journal of the American Chemical Society, Vol. 58, Issue 8 https://doi.org/10.1021/ja01299a050	journal	August 1936
Potential-dependent water orientation: an in situ spectroscopic study Habib, M. A.; Bockris, J. O. Langmuir, Vol. 2, Issue 4 https://doi.org/10.1021/la00070a003	journal	July 1986
Molecular-level origin of the carboxylate head group response to divalent metal ion complexation at the air–water interface Denton, Joanna K.; Kelleher, Patrick J.; Johnson, Mark A. Proceedings of the National Academy of Sciences, Vol. 116, Issue 30 https://doi.org/10.1073/pnas.1818600116	journal	July 2019
Hidden role of intermolecular proton transfer in the anomalously diffuse vibrational spectrum of a trapped hydronium ion Craig, Stephanie M.; Menges, Fabian S.; Duong, Chinh H. Proceedings of the National Academy of Sciences, Vol. 114, Issue 24 https://doi.org/10.1073/pnas.1705089114	journal	May 2017
Coordination-Dependent Spectroscopic Signatures of Divalent Metal Ion Binding to Carboxylate Head Groups: H ₂ - and He-Tagged Vibrational Spectra of M ²⁺ ·RCO ₂ ¯ (M = Mg and Ca, R = −CD ₃ , −CD ₂ CD ₃ ) Complexes DePalma, Joseph W.; Kelleher, Patrick J.; Tavares, Laís C. The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02964	journal	January 2017
Spectroscopic Characterization of Solvent-Mediated Folding in Dicarboxylate Dianions Wende, Torsten; Wanko, Marius; Jiang, Ling Angewandte Chemie International Edition, Vol. 50, Issue 16 https://doi.org/10.1002/anie.201006485	journal	March 2011
Argon predissociation and electron autodetachment spectroscopy of size-selected CH3NO2−⋅Arn clusters Weber, J. M.; Robertson, W. H.; Johnson, M. A. The Journal of Chemical Physics, Vol. 115, Issue 23 https://doi.org/10.1063/1.1418251	journal	December 2001
Microhydration of Nitromethane Anions from Both a Solute and Solvent Perspective Marcum, Jesse C.; Weber, J. Mathias The Journal of Physical Chemistry A, Vol. 114, Issue 34 https://doi.org/10.1021/jp103682q	journal	September 2010
Infrared spectra of the cluster ions H ₇ O ⁺ ₃ ⋅H ₂ and H ₉ O ⁺ ₄ ⋅H ₂ Okumura, M.; Yeh, L. I.; Myers, J. D. The Journal of Chemical Physics, Vol. 85, Issue 4 https://doi.org/10.1063/1.451079	journal	August 1986
Cryogenic Ion Chemistry and Spectroscopy Wolk, Arron B.; Leavitt, Christopher M.; Garand, Etienne Accounts of Chemical Research, Vol. 47, Issue 1 https://doi.org/10.1021/ar400125a	journal	August 2013
A pulsed supersonic entrainment reactor for the rational preparation of cold ionic complexes Robertson, W. H.; Kelley, J. A.; Johnson, M. A. Review of Scientific Instruments, Vol. 71, Issue 12 https://doi.org/10.1063/1.1326931	journal	January 2000
Infrared Signatures of a Water Molecule Attached to Triatomic Domains of Molecular Anions: Evolution of the H-bonding Configuration with Domain Length Robertson, William H.; Price, Erica A.; Weber, J. Mathias The Journal of Physical Chemistry A, Vol. 107, Issue 34 https://doi.org/10.1021/jp030474v	journal	August 2003
Note on an Approximation Treatment for Many-Electron Systems Møller, Chr.; Plesset, M. S. Physical Review, Vol. 46, Issue 7 https://doi.org/10.1103/PhysRev.46.618	journal	October 1934
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Bonded-atom fragments for describing molecular charge densities Hirshfeld, F. L. Theoretica Chimica Acta, Vol. 44, Issue 2 https://doi.org/10.1007/BF00549096	journal	January 1977
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis Vosko, S. H.; Wilk, L.; Nusair, M. Canadian Journal of Physics, Vol. 58, Issue 8 https://doi.org/10.1139/p80-159	journal	August 1980
Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F. The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627 https://doi.org/10.1021/j100096a001	journal	November 1994
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Theoretical Study on the Excess Electron Binding Mechanism in the [CH ₃ NO ₂ ·(H ₂ O) _n ] ⁻ ( n = 1−6) Anion Clusters Motegi, Haruki; Takayanagi, Toshiyuki; Tsuneda, Takao The Journal of Physical Chemistry A, Vol. 114, Issue 34 https://doi.org/10.1021/jp1041124	journal	September 2010
Infrared photodissociation spectroscopy of D ₂ -tagged CH ₃ CO ₂ ⁻ (H ₂ O) ₀₋₂ anions DeVine, Jessalyn A.; Debnath, Sreekanta; Li, Ya-Ke Molecular Physics, Vol. 118, Issue 11 https://doi.org/10.1080/00268976.2020.1749953	journal	April 2020
Isolation of site-specific anharmonicities of individual water molecules in the I − ·(H 2 O) 2 complex using tag-free, isotopomer selective IR-IR double resonance Yang, Nan; Duong, Chinh H.; Kelleher, Patrick J. Chemical Physics Letters, Vol. 690 https://doi.org/10.1016/j.cplett.2017.09.042	journal	December 2017
M OLECULAR A SPECTS OF H ALIDE I ON H YDRATION : The Cluster Approach Robertson, William H.; Johnson, Mark A. Annual Review of Physical Chemistry, Vol. 54, Issue 1 https://doi.org/10.1146/annurev.physchem.54.011002.103801	journal	October 2003
Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy Perez, C.; Muckle, M. T.; Zaleski, D. P. Science, Vol. 336, Issue 6083 https://doi.org/10.1126/science.1220574	journal	May 2012
Large anharmonic effects in the infrared spectra of the symmetrical CH3NO2−⋅(H2O) and CH3CO2−⋅(H2O) complexes Myshakin, Evgeniy M.; Jordan, Kenneth D.; Sibert, Edwin L. The Journal of Chemical Physics, Vol. 119, Issue 19 https://doi.org/10.1063/1.1616918	journal	November 2003
Nonadiabatic vibrational dynamics in the HCO2−⋅H2O complex Hamm, Peter; Stock, Gerhard The Journal of Chemical Physics, Vol. 143, Issue 13 https://doi.org/10.1063/1.4932189	journal	October 2015
Vibrational Spectroscopy of the Water–Nitrate Complex in the O–H Stretching Region Heine, Nadja; Kratz, Eric G.; Bergmann, Risshu The Journal of Physical Chemistry A, Vol. 118, Issue 37 https://doi.org/10.1021/jp500964j	journal	April 2014
Two-Dimensional Adiabatic Model for Calculating Progressions Resulting from Stretch–Rock Coupling in Vibrational Spectra of Anion–Water Complexes Henderson, Elva V.; Jordan, Kenneth D. The Journal of Physical Chemistry Letters, Vol. 12, Issue 27 https://doi.org/10.1021/acs.jpclett.1c01625	journal	July 2021
Disentangling the Complex Vibrational Mechanics of the Protonated Water Trimer by Rational Control of Its Hydrogen Bonds Duong, Chinh H.; Yang, Nan; Johnson, Mark A. The Journal of Physical Chemistry A, Vol. 123, Issue 37 https://doi.org/10.1021/acs.jpca.9b05576	journal	August 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 Duong, Chinh H.; Yang, Nan; Kelleher, Patrick J. The Journal of Physical Chemistry A, Vol. 122, Issue 48 https://doi.org/10.1021/acs.jpca.8b08507	journal	October 2018
Unmasking Rare, Large-Amplitude Motions in D ₂ -Tagged I ^– ·(H ₂ O) ₂ Isotopomers with Two-Color, Infrared–Infrared Vibrational Predissociation Spectroscopy Yang, Nan; Duong, Chinh H.; Kelleher, Patrick J. The Journal of Physical Chemistry Letters, Vol. 9, Issue 13 https://doi.org/10.1021/acs.jpclett.8b01485	journal	June 2018
Hydrogen Bond Cooperativity and the Three-Dimensional Structures of Water Nonamers and Decamers Pérez, Cristóbal; Zaleski, Daniel P.; Seifert, Nathan A. Angewandte Chemie International Edition, Vol. 53, Issue 52 https://doi.org/10.1002/anie.201407447	journal	October 2014
Infrared Spectrum of a Molecular Ice Cube: The S4 and D2d Water Octamers in Benzene-(Water)8 Gruenloh, C. J. Science, Vol. 276, Issue 5319 https://doi.org/10.1126/science.276.5319.1678	journal	June 1997
Solvation of the Cl ^- ·H ₂ O Complex in CCl ₄ Clusters: The Effect of Solvent-Mediated Charge Redistribution on the Ionic H-Bond Robertson, William H.; Weddle, Gary H.; Kelley, Jude A. The Journal of Physical Chemistry A, Vol. 106, Issue 7 https://doi.org/10.1021/jp0137468	journal	January 2002
Local Mode Approach to OH Stretch Spectra of Benzene–(H ₂ O) _n Clusters, n = 2–7 Tabor, Daniel P.; Kusaka, Ryoji; Walsh, Patrick S. The Journal of Physical Chemistry A, Vol. 119, Issue 38 https://doi.org/10.1021/acs.jpca.5b06954	journal	August 2015
IR and SFG vibrational spectroscopy of the water bend in the bulk liquid and at the liquid-vapor interface, respectively Ni, Yicun; Skinner, J. L. The Journal of Chemical Physics, Vol. 143, Issue 1 https://doi.org/10.1063/1.4923462	journal	July 2015
Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters Yang, Nan; Khuu, Thien; Mitra, Sayoni The Journal of Physical Chemistry A, Vol. 124, Issue 50 https://doi.org/10.1021/acs.jpca.0c07795	journal	December 2020
Spectroscopic Determination of the OH- Solvation Shell in the OH-middle dot(H2O)n Clusters Robertson, W. H. Science, Vol. 299, Issue 5611 https://doi.org/10.1126/science.1080695	journal	January 2003
Water network-mediated, electron-induced proton transfer in [C5H5N ⋅ (H2O)n]− clusters DeBlase, Andrew F.; Wolke, Conrad T.; Weddle, Gary H. The Journal of Chemical Physics, Vol. 143, Issue 14 https://doi.org/10.1063/1.4931928	journal	October 2015
Vibrational Spectroscopy of Nitroalkane Chains Using Electron Autodetachment and Ar Predissociation Schneider, Holger; Vogelhuber, Kristen M.; Schinle, Florian The Journal of Physical Chemistry A, Vol. 112, Issue 33 https://doi.org/10.1021/jp800124s	journal	August 2008
On the binding of electrons to nitromethane: Dipole and valence bound anions Compton, R. N.; Carman, H. S.; Desfrançois, C. The Journal of Chemical Physics, Vol. 105, Issue 9 https://doi.org/10.1063/1.472993	journal	September 1996
Ab initio study on radical anions of nitro compounds Ramondo, Fabio Canadian Journal of Chemistry, Vol. 70, Issue 2 https://doi.org/10.1139/v92-045	journal	February 1992
Theoretical and spectroscopic study of asymmetric methyl rotor dynamics in gaseous partially deuterated nitromethanes Gorse, Dominique; Cavagnat, Dominique; Pesquer, Michel The Journal of Physical Chemistry, Vol. 97, Issue 17 https://doi.org/10.1021/j100119a005	journal	April 1993
Vibrational spectra of nitromethanes and the effects of internal rotation McKean, D. C.; Watt, R. A. Journal of Molecular Spectroscopy, Vol. 61, Issue 2 https://doi.org/10.1016/0022-2852(76)90241-1	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 Gerardi, Helen K.; DeBlase, Andrew F.; Su, Xiaoge The Journal of Physical Chemistry Letters, Vol. 2, Issue 19 https://doi.org/10.1021/jz200937v	journal	September 2011
Gas-Phase Spectroscopic Signatures of Carboxylate–Li ⁺ Contact Ion Pairs: New Benchmarks For Characterizing Ion Pairing in Solution Habka, Sana; Brenner, Valérie; Mons, Michel The Journal of Physical Chemistry Letters, Vol. 7, Issue 7 https://doi.org/10.1021/acs.jpclett.6b00454	journal	March 2016
Low-energy photoelectron imaging spectroscopy of nitromethane anions: Electron affinity, vibrational features, anisotropies, and the dipole-bound state Adams, Christopher L.; Schneider, Holger; Ervin, Kent M. The Journal of Chemical Physics, Vol. 130, Issue 7 https://doi.org/10.1063/1.3076892	journal	February 2009
Laser photoelectron spectroscopy of the formyl anion Murray, Kermit K.; Miller, Thomas M.; Leopold, Doreen G. The Journal of Chemical Physics, Vol. 84, Issue 5 https://doi.org/10.1063/1.450371	journal	March 1986

Similar Records

Microsolvation in V⁺(H₂O)_n Clusters Studied with Selected-Ion Infrared Spectroscopy

Journal Article · Tue Jan 21 00:00:00 EST 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1864713

Carnegie, Prosser D.; Marks, Joshua H.; Brathwaite, Antonio D.; +2 more

Isotopomer-selective spectra of a single intact H₂O molecule in the Cs⁺(D₂O)₅H₂O isotopologue: Going beyond pattern recognition to harvest the structural information encoded in vibrational spectra

Journal Article · Wed Feb 17 00:00:00 EST 2016 · Journal of Chemical Physics · OSTI ID:1864713

Wolke, Conrad T.; Fournier, Joseph A.; Miliordos, Evangelos; +3 more

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 Article · Sat Mar 05 00:00:00 EST 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory · OSTI ID:1864713

Mitra, Sayoni; Khuu, Thien; Choi, Tae Hoon; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Molecular structure
Cluster chemistry
Ions
Molecules

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

Citation Formats

References (52)

Similar Records

Related Subjects

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