The selenocyanate dimer radical anion in water: Transient Raman spectra, structure, and reaction dynamics
Abstract
The selenocyanate dimer radical anion (SeCN)2•-, prepared by electron pulse irradiation of selenocyanate anion (SeCN)⁻ in water, has been examined by transient absorption, time-resolved Raman spectra, and range-separated hybrid density functional (ωB97x and LC-ωPBE) theory. The Raman spectrum, excited in resonance with the 450 nm (λmax) absorption of the radical, is dominated by a very strong band at 140.5 cm⁻¹, associated with the Se–Se stretching vibration, its overtones and combinations. A striking feature of the (SeCN)2•- Raman spectrum is the relative sharpness of the 140.5 cm⁻¹ band compared to the S–S band at 220 cm⁻¹ in thiocyanate radical anion (SCN)2•-, the difference of which is explained in terms of a time-averaged site effect. Calculations, which reproduce experimental frequencies fairly well, predict a molecular geometry with the SeSe bond length of 2.917 (±0.04) Å, the SeC bond length of 1.819 (±0.004) Å, and the CN bond length of 1.155 (±0.002) Å. An anharmonicity of 0.44 cm⁻¹ has been determined for the 140.5 cm⁻¹ Se–Se vibration which led to a dissociation energy of -1.4 eV for the SeSe bond, using the Morse potential in a diatomic approximation. This value, estimated for the radical confined in a solvent cage, compares well with themore »
- Authors:
-
- Univ. of Notre Dame, IN (United States)
- Publication Date:
- Research Org.:
- University of Notre Dame, IN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1609174
- Grant/Contract Number:
- FC02-04ER15533
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 150; Journal Issue: 9; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics; Radicals (Chemistry); Spastic Syndrome; Selenocyanate; 5-Phenylcarbamoylpentyl Selenocyanide; Cholecystectomy, Laparoscopic; Structure; Probe Gene Fragment; Solvents; Selenium Supplement; 3,5,5-Trimethyl-2-Morpholinon-3-Yl Radical Dimer
Citation Formats
Janik, Ireneusz, and Tripathi, G. N. R. The selenocyanate dimer radical anion in water: Transient Raman spectra, structure, and reaction dynamics. United States: N. p., 2019.
Web. doi:10.1063/1.5086400.
Janik, Ireneusz, & Tripathi, G. N. R. The selenocyanate dimer radical anion in water: Transient Raman spectra, structure, and reaction dynamics. United States. https://doi.org/10.1063/1.5086400
Janik, Ireneusz, and Tripathi, G. N. R. Tue .
"The selenocyanate dimer radical anion in water: Transient Raman spectra, structure, and reaction dynamics". United States. https://doi.org/10.1063/1.5086400. https://www.osti.gov/servlets/purl/1609174.
@article{osti_1609174,
title = {The selenocyanate dimer radical anion in water: Transient Raman spectra, structure, and reaction dynamics},
author = {Janik, Ireneusz and Tripathi, G. N. R.},
abstractNote = {The selenocyanate dimer radical anion (SeCN)2•-, prepared by electron pulse irradiation of selenocyanate anion (SeCN)⁻ in water, has been examined by transient absorption, time-resolved Raman spectra, and range-separated hybrid density functional (ωB97x and LC-ωPBE) theory. The Raman spectrum, excited in resonance with the 450 nm (λmax) absorption of the radical, is dominated by a very strong band at 140.5 cm⁻¹, associated with the Se–Se stretching vibration, its overtones and combinations. A striking feature of the (SeCN)2•- Raman spectrum is the relative sharpness of the 140.5 cm⁻¹ band compared to the S–S band at 220 cm⁻¹ in thiocyanate radical anion (SCN)2•-, the difference of which is explained in terms of a time-averaged site effect. Calculations, which reproduce experimental frequencies fairly well, predict a molecular geometry with the SeSe bond length of 2.917 (±0.04) Å, the SeC bond length of 1.819 (±0.004) Å, and the CN bond length of 1.155 (±0.002) Å. An anharmonicity of 0.44 cm⁻¹ has been determined for the 140.5 cm⁻¹ Se–Se vibration which led to a dissociation energy of -1.4 eV for the SeSe bond, using the Morse potential in a diatomic approximation. This value, estimated for the radical confined in a solvent cage, compares well with the calculated gas-phase energy, 1.32 ± 0.04 eV, required for the radical to dissociate into (SeCN)• and (SeCN)⁻ fragments. Here, the enthalpy of dissociation in water has been measured (0.36 eV) and compared with the value estimated by accounting for the solvent dielectric effects in structural calculations.},
doi = {10.1063/1.5086400},
journal = {Journal of Chemical Physics},
number = 9,
volume = 150,
place = {United States},
year = {Tue Mar 05 00:00:00 EST 2019},
month = {Tue Mar 05 00:00:00 EST 2019}
}
Web of Science
Works referenced in this record:
Assessment of a long-range corrected hybrid functional
journal, December 2006
- Vydrov, Oleg A.; Scuseria, Gustavo E.
- The Journal of Chemical Physics, Vol. 125, Issue 23
Resonance Raman spectra of the transient Cl− and Br− radical anions
journal, May 1984
- Wilbrandt, Robert; Jensen, Niels-Henrik; Sillesen, Alfred H.
- Chemical Physics Letters, Vol. 106, Issue 6
Time-resolved study on the reactions of organic selenides with hydroxyl and oxide radicals, hydrated electrons, and H-atoms in aqueous solution, and DFT calculations of transients in comparison with sulfur analogues
journal, January 2010
- Tobien, Thomas; Bonifačić, Marija; Naumov, Sergej
- Physical Chemistry Chemical Physics, Vol. 12, Issue 25
Picosecond Pulse Radiolysis of Direct and Indirect Radiolytic Effects in Highly Concentrated Halide Aqueous Solutions
journal, August 2011
- Balcerzyk, Anna; Schmidhammer, Uli; El Omar, Abdel Karim
- The Journal of Physical Chemistry A, Vol. 115, Issue 33
Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post- d group 16–18 elements
journal, December 2003
- Peterson, Kirk A.; Figgen, Detlev; Goll, Erich
- The Journal of Chemical Physics, Vol. 119, Issue 21
The role of databases in support of computational chemistry calculations
journal, October 1996
- Feller, David
- Journal of Computational Chemistry, Vol. 17, Issue 13
The Nature of the Chemical Bond. ii. the One-Electron bond and the Three-Electron bond
journal, September 1931
- Pauling, Linus.
- Journal of the American Chemical Society, Vol. 53, Issue 9
Scavenging of e s − and OH radicals in concentrated HCl and NaCl aqueous solutions
journal, July 2008
- Atinault, E.; De Waele, V.; Schmidhammer, U.
- Chemical Physics Letters, Vol. 460, Issue 4-6
Proton Reactivity and Electronic Structure of Phenoxyl Radicals in Water †
journal, March 1998
- Tripathi, G. N. R.
- The Journal of Physical Chemistry A, Vol. 102, Issue 13
Transient Raman spectra, structure, and thermochemistry of the thiocyanate dimer radical anion in water
journal, June 2017
- Janik, Ireneusz; Carmichael, Ian; Tripathi, G. N. R.
- The Journal of Chemical Physics, Vol. 146, Issue 21
Resonance Raman spectrum of the transient (SCN)−2 free radical anion
journal, January 1979
- Wilbrandt, R.; Jensen, N. H.; Pagsberg, P.
- Chemical Physics Letters, Vol. 60, Issue 2
253. The tellurocyanate ion, TeCN?
journal, January 1964
- Greenwood, N. N.; Little, R.; Sprague, M. J.
- Journal of the Chemical Society (Resumed)
The nature of the CO2− radical anion in water
journal, April 2016
- Janik, Ireneusz; Tripathi, G. N. R.
- The Journal of Chemical Physics, Vol. 144, Issue 15
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
Water-anion hydrogen bonding dynamics: Ultrafast IR experiments and simulations
journal, June 2017
- Yamada, Steven A.; Thompson, Ward H.; Fayer, Michael D.
- The Journal of Chemical Physics, Vol. 146, Issue 23
Basis Set Exchange: A Community Database for Computational Sciences
journal, March 2007
- Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd
- Journal of Chemical Information and Modeling, Vol. 47, Issue 3
Odd-electron .sigma. bonds
journal, March 1988
- Clark, Timothy.
- Journal of the American Chemical Society, Vol. 110, Issue 6
The nature of the superoxide radical anion in water
journal, July 2013
- Janik, Ireneusz; Tripathi, G. N. R.
- The Journal of Chemical Physics, Vol. 139, Issue 1
Oxidation of Bromide Ions by Hydroxyl Radicals: Spectral Characterization of the Intermediate BrOH •–
journal, January 2013
- Lampre, Isabelle; Marignier, Jean-Louis; Mirdamadi-Esfahani, Malaknaz
- The Journal of Physical Chemistry A, Vol. 117, Issue 5
Pulse radiolysis of aqueous thiocyanate solutions. Nature of the intermediate transient species
journal, May 1972
- Behar, D.; Bevan, P. L. T.; Scholes, G.
- The Journal of Physical Chemistry, Vol. 76, Issue 11
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993
- Woon, David E.; Dunning, Thom H.
- The Journal of Chemical Physics, Vol. 98, Issue 2
The early events in the OH radical oxidation of dimethyl sulfide in water
journal, January 2013
- Janik, Ireneusz; Tripathi, G. N. R.
- The Journal of Chemical Physics, Vol. 138, Issue 4
Time‐resolved resonance Raman study of the spectroscopy and kinetics of the Cl − 2 radical anion in aqueous solution
journal, September 1988
- Hynes, A. J.; Wine, P. H.
- The Journal of Chemical Physics, Vol. 89, Issue 6
Quantum Mechanical Continuum Solvation Models
journal, October 2005
- Tomasi, Jacopo; Menucci, Benedetta; Cammi, Roberto
- ChemInform, Vol. 36, Issue 42
Quantum Mechanical Continuum Solvation Models
journal, August 2005
- Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
- Chemical Reviews, Vol. 105, Issue 8
Transient Raman Spectra, Structure and Thermochemistry of the Thiocyanate Dimer Radical Anion in Water
conference, June 2017
- Janik, Ireneusz; Carmichael, Ian; Tripathi, G.
- Proceedings of the 72nd International Symposium on Molecular Spectroscopy
Polyhalide radical anions as intermediates in chemistry
journal, May 1981
- de Violet, Ph. Fornier
- Reviews of Chemical Intermediates, Vol. 4, Issue 1-4
Time-resolved resonance raman spectra of dihalide radical anions in aqueous solution
journal, February 1985
- Tripathi, G. N. R.; Schuler, R. H.; Fessenden, R. W.
- Chemical Physics Letters, Vol. 113, Issue 6
Isolation and reversible dimerization of a selenium–selenium three-electron σ-bond
journal, June 2014
- Zhang, Senwang; Wang, Xingyong; Su, Yuanting
- Nature Communications, Vol. 5, Issue 1
Vibrational analysis of (SCN) 2 and the transient (SCN) 2 −
journal, October 1979
- Jensen, N. H.; Wilbrandt, R.; Pagsberg, P.
- The Journal of Chemical Physics, Vol. 71, Issue 8
Critical Review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (⋅OH/⋅O − in Aqueous Solution
journal, April 1988
- Buxton, George V.; Greenstock, Clive L.; Helman, W. Phillips
- Journal of Physical and Chemical Reference Data, Vol. 17, Issue 2
Glossary of class names of organic compounds and reactivity intermediates based on structure (IUPAC Recommendations 1995)
journal, January 1995
- Moss, G. P.; Smith, P. A. S.; Tavernier, D.
- Pure and Applied Chemistry, Vol. 67, Issue 8-9