Solvated Electron in Acetonitrile: Radiation Yield, Absorption Spectrum, and Equilibrium between Cavity- and Solvent-Localized States

Grills, David C.; Lymar, Sergei V.

doi:10.1021/acs.jpcb.1c08946

Solvated Electron in Acetonitrile: Radiation Yield, Absorption Spectrum, and Equilibrium between Cavity- and Solvent-Localized States

Journal Article · Tue Dec 21 00:00:00 EST 2021 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.1c08946· OSTI ID:1837211

^[1]; Lymar, Sergei V. ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)

The equilibrium between a solvent cavity-localized electron, ecav-, and a dimeric solvent anion, (CH₃CN)$$_{2}^{•-}$$, which are the two lowest energy states of the solvated electron in acetonitrile, has been investigated by pulse radiolysis at 233-353 K. The enthalpy and entropy for the e$$_{cav}^{-}$$ to (CH₃CN)$$_{2}^{•-}$$ conversion amount to -11.2 ± 0.3 kcal/mol and -39.3 ± 1.2 cal/(mol K), corresponding to a 0.44 ± 0.35 equilibrium constant at 25 °C. The radiation yield of the solvated electron has been quantified using a Co(II) macrocycle that scavenges electrons with a 1.55 × 10¹¹ M^-1 s^-1 rate constant. The apparent yield increases without saturation over the attainable scavenger concentration range, reaching 2.8 per 100 eV; this value represents the lower limit for the acetonitrile ionization yield in pulse radiolysis. The apparent molar absorption coefficient of (20.8 ± 1.5) × 10³ M^-1 cm^-1 at 1450 nm and 20 °C for the solvated electron and individual vis-near-infrared (NIR) absorption spectra of e$$_{cav}^{-}$$ and (CH₃CN)$$_{2}^{•-}$$ are derived from the data. Variances with previous reports are thoroughly discussed. All together, these results resolve several controversies concerning the solvated electron properties in acetonitrile and furnish requisite data for quantitative pulse radiolysis investigations in this commonly used solvent.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1837211

Report Number(s):: BNL--222531-2021-JAAM

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 1 Vol. 126; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (39)

Solvated electron in acetonitrile Singh, A.; Gesser, H. D.; Scott, A. R. Chemical Physics Letters, Vol. 2, Issue 5 https://doi.org/10.1016/0009-2614(68)80071-5	journal	September 1968
Electron-solvent interaction: Attachment solvation competition Belloni, J.; Marignier, J. L. International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry, Vol. 34, Issue 1 https://doi.org/10.1016/1359-0197(89)90020-9	journal	January 1989
Theoretical simulations of dynamics of excess electron attachment to acetonitrile clusters Takayanagi, Toshiyuki Chemical Physics, Vol. 302, Issue 1-3 https://doi.org/10.1016/j.chemphys.2004.03.020	journal	July 2004
Electronic structure calculations of acetonitrile cluster anions: Stabilization mechanism of molecular radical anions by solvation Takayanagi, Toshiyuki; Hoshino, Tetsuya; Takahashi, Kenta Chemical Physics, Vol. 324, Issue 2-3 https://doi.org/10.1016/j.chemphys.2005.12.005	journal	May 2006
Time-resolved dynamics in acetonitrile cluster anions (CH3CN)n- Young, Ryan M.; Griffin, Graham B.; Kammrath, Aster Chemical Physics Letters, Vol. 485, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.12.058	journal	January 2010
Ab Initio Simulations of Poorly and Well Equilibrated (CH ₃ CN) _n ^– Cluster Anions: Assigning Experimental Photoelectron Peaks to Surface-Bound Electrons and Solvated Monomer and Dimer Anions Narvaez, Wilberth A.; Schwartz, Benjamin J. The Journal of Physical Chemistry A, Vol. 125, Issue 35 https://doi.org/10.1021/acs.jpca.1c05855	journal	August 2021
Radical Ions of 3-Styryl-quinoxalin-2-one Derivatives Studied by Pulse Radiolysis in Organic Solvents Skotnicki, Konrad; De la Fuente, Julio R.; Cañete, Álvaro The Journal of Physical Chemistry B, Vol. 122, Issue 14 https://doi.org/10.1021/acs.jpcb.8b01004	journal	March 2018
Solution studies of the cobalt(II) N-rac- and N-meso-Col2+ isomers and molecular and crystal structures of the low-spin, five-coordinate cobalt(II) macrocyclic complexes N-rac-[CoL(H2O)](ClO4)2.cntdot.0.6H2O (1) and N-rac-[CoL(OC103)]ClO4 (2) (L = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4, 11-diene) Szalda, David J.; Schwarz, Carolyn L.; Endicott, John F. Inorganic Chemistry, Vol. 28, Issue 16 https://doi.org/10.1021/ic00315a026	journal	August 1989
Radiolytic studies of ruthenium oxo-acetato trinuclear complexes in acetonitrile Imamura, Taira; Sumiyoshi, Takashi; Takahashi, Kenta The Journal of Physical Chemistry, Vol. 97, Issue 29 https://doi.org/10.1021/j100131a058	journal	July 1993
Transient phenomena in the pulse radiolysis of retinyl polyenes. 4. Environmental effects on absorption maximum of retinal radical anion Bobrowski, K.; Das, P. K. The Journal of Physical Chemistry, Vol. 89, Issue 26 https://doi.org/10.1021/j100272a032	journal	December 1985
Effect of pressure on the electron mobility in liquid benzene and toluene Itoh, Kengo.; Holroyd, Richard. The Journal of Physical Chemistry, Vol. 94, Issue 25 https://doi.org/10.1021/j100388a020	journal	December 1990
Shapes of optical spectra of solvated electrons. Effect of pressure Jou, Fang-Yuan; Freeman, Gordon R. The Journal of Physical Chemistry, Vol. 81, Issue 9 https://doi.org/10.1021/j100524a021	journal	May 1977
Optical spectra and reactivities of radical anions of 4-nitrobenzyl compounds produced by pulse radiolysis of acetonitrile solutions Burrows, H. D.; Kosower, Edward M. The Journal of Physical Chemistry, Vol. 78, Issue 2 https://doi.org/10.1021/j100595a006	journal	January 1974
Thermodynamics and kinetics of carbon dioxide binding to two stereoisomers of a cobalt(I) macrocycle in aqueous solution Creutz, Carol; Schwarz, Harold A.; Wishart, James F. Journal of the American Chemical Society, Vol. 113, Issue 9 https://doi.org/10.1021/ja00009a022	journal	April 1991
Carbon dioxide activation: thermodynamics of carbon dioxide binding and the involvement of two cobalt centers in the reduction of carbon dioxide by a cobalt(I) macrocycle Fujita, Etsuko.; Szalda, David J.; Creutz, Carol. Journal of the American Chemical Society, Vol. 110, Issue 14 https://doi.org/10.1021/ja00222a079	journal	July 1988
The reactivity of cobalt(I) complexes containing unsaturated macrocyclic ligands in aqueous solution Tait, A. Martin; Hoffman, Morton Z.; Hayon, E. Journal of the American Chemical Society, Vol. 98, Issue 1 https://doi.org/10.1021/ja00417a015	journal	January 1976
Mechanism of the Formation of a Mn-Based CO ₂ Reduction Catalyst Revealed by Pulse Radiolysis with Time-Resolved Infrared Detection Grills, David C.; Farrington, Jaime A.; Layne, Bobby H. Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja501051s	journal	April 2014
Electron Localization in Liquid Acetonitrile Shkrob, I. A.; Sauer, M. C. The Journal of Physical Chemistry A, Vol. 106, Issue 39 https://doi.org/10.1021/jp0207580	journal	October 2002
Electron Localization in Solid Acetonitrile Shkrob, Ilya A.; Takeda, Keiji; Williams, Ffrancon The Journal of Physical Chemistry A, Vol. 106, Issue 39 https://doi.org/10.1021/jp020759s	journal	August 2002
Electronic Structure of the Acetonitrile and Acetonitrile Dimer Anions: A Topological Investigation Timerghazin, Qadir K.; Peslherbe, Gilles H. The Journal of Physical Chemistry B, Vol. 112, Issue 2 https://doi.org/10.1021/jp0774948	journal	December 2007
Ultrafast Studies of Excess Electrons in Liquid Acetonitrile: Revisiting the Solvated Electron/Solvent Dimer Anion Equilibrium Doan, Stephanie C.; Schwartz, Benjamin J. The Journal of Physical Chemistry B, Vol. 117, Issue 16 https://doi.org/10.1021/jp303591h	journal	July 2012
Transient Phenomena in the Pulse Radiolysis of Oxoisoaporphine Derivatives in Acetonitrile De la Fuente, Julio R.; Kciuk, Gabriel; Sobarzo-Sanchez, Eduardo The Journal of Physical Chemistry A, Vol. 112, Issue 41 https://doi.org/10.1021/jp804470c	journal	October 2008
Solvated Electron Extinction Coefficient and Oscillator Strength in High Temperature Water ^† Hare, Patrick M.; Price, Erica A.; Stanisky, Christopher M. The Journal of Physical Chemistry A, Vol. 114, Issue 4 https://doi.org/10.1021/jp909789b	journal	February 2010
Nature of Excess Electrons in Polar Fluids: Anion-Solvated Electron Equilibrium and Polarized Hole-Burning in Liquid Acetonitrile Doan, Stephanie C.; Schwartz, Benjamin J. The Journal of Physical Chemistry Letters, Vol. 4, Issue 9 https://doi.org/10.1021/jz400621m	journal	April 2013
Radiolytic formation of the carbon dioxide radical anion in acetonitrile revealed by transient IR spectroscopy Grills, David C.; Lymar, Sergei V. Physical Chemistry Chemical Physics, Vol. 20, Issue 15 https://doi.org/10.1039/C8CP00977E	journal	January 2018
Time-dependent yield of the hydrated electron and the hydroxyl radical in D ₂ O: a picosecond pulse radiolysis study Wang, Furong; Schmidhammer, Uli; Larbre, Jean-Philippe Physical Chemistry Chemical Physics, Vol. 20, Issue 23 https://doi.org/10.1039/C8CP02276C	journal	January 2018
Pulse radiolyses of anthraquinone and anthraquinone–triethylamine in acetonitrile and toluene at room temperature Nakayama, Toshihiro; Ushida, Kiminori; Hamanoue, Kumao J. Chem. Soc., Faraday Trans., Vol. 86, Issue 1 https://doi.org/10.1039/FT9908600095	journal	January 1990
Characterization of electronically excited states in anionic acetonitrile clusters Azar, Julian; Kurlancheek, Westin; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 13, Issue 20 https://doi.org/10.1039/c1cp20089e	journal	January 2011
Photoelectron spectroscopy of solvated electrons in alcohol and acetonitrile microjets Shreve, Alexander T.; Elkins, Madeline H.; Neumark, Daniel M. Chemical Science, Vol. 4, Issue 4 https://doi.org/10.1039/c3sc22063j	journal	January 2013
Solute ion and radical formation in the pulse radiolysis of acetonitrile solutions Baptista, João L.; Burrows, Hugh D. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 70, Issue 0 https://doi.org/10.1039/f19747002066	journal	January 1974
Kinetic and thermodynamic character of reducing species produced on pulse radiolysis of acetonitrile Bell, Ian P.; Rodgers, Michael A. J.; Burrows, Hugh D. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777300315	journal	January 1977
Photoinduced electron transfer from aliphatic amines to coumarin dyes Nad, Sanjukta; Pal, Haridas The Journal of Chemical Physics, Vol. 116, Issue 4 https://doi.org/10.1063/1.1415451	journal	January 2002
Femtosecond electron ejection in liquid acetonitrile: Evidence for cavity electrons and solvent anions Xia, Chungeng; Peon, Jorge; Kohler, Bern The Journal of Chemical Physics, Vol. 117, Issue 19 https://doi.org/10.1063/1.1513152	journal	November 2002
Yield of Ions and Excited States Produced in the Radiolysis of Polar Organic Liquids Hayon, E. The Journal of Chemical Physics, Vol. 53, Issue 6 https://doi.org/10.1063/1.1674332	journal	September 1970
The LEAF picosecond pulse radiolysis facility at Brookhaven National Laboratory Wishart, James F.; Cook, Andrew R.; Miller, John R. Review of Scientific Instruments, Vol. 75, Issue 11 https://doi.org/10.1063/1.1807004	journal	November 2004
Ab initio study of small acetonitrile cluster anions Takayanagi, Toshiyuki The Journal of Chemical Physics, Vol. 122, Issue 24 https://doi.org/10.1063/1.1944722	journal	June 2005
Coexistence of Solvated Electrons and Solvent Valence Anions in Negatively Charged Acetonitrile Clusters, ( C H 3 C N ) n − ( n = 10 – 100 ) Mitsui, Masaaki; Ando, Naoto; Kokubo, Shinsuke Physical Review Letters, Vol. 91, Issue 15 https://doi.org/10.1103/PhysRevLett.91.153002	journal	October 2003
Electron attachment to amides studied by low-pressure chemical ionization and electron swarms: comparison of the gas and liquid phase Tran-Thi, T. H.; Koulkès-Pujo, A. M. Canadian Journal of Physics, Vol. 63, Issue 5 https://doi.org/10.1139/p85-088	journal	May 1985
Spectroscopic properties of anion radicals studied using pulse radiolysis Samant, Vaishali; Singh, Ajay K.; Mukherjee, Tulsi Research on Chemical Intermediates, Vol. 32, Issue 8 https://doi.org/10.1163/156856706778606499	journal	August 2006

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38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Pulse radiolysis
acetonitrile
equilibrium
radiation chemistry
solvated electron

Solvated Electron in Acetonitrile: Radiation Yield, Absorption Spectrum, and Equilibrium between Cavity- and Solvent-Localized States

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