New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk

Bhattacharyya, Dhritiman; Mizuno, Hikaru; Rizzuto, Anthony M.; Zhang, Yuyuan; Saykally, Richard J.; Bradforth, Stephen E.

doi:10.1021/acs.jpclett.9b03857

Title: New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk

Journal Article · Mon Feb 10 00:00:00 EST 2020 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.9b03857· OSTI ID:1601227

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^[3]; Zhang, Yuyuan ^[1];

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Univ. of Southern California, Los Angeles, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Elon Univ., Elon, NC (United States)

Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. Here in this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin–orbit split iodine states, ²P_3/2 and ²P_1/2. In the 2PA spectra, the lower-energy ²P_3/2 peak is absent and the observed 2PA peak, which is ~0.14 eV blue-shifted relative to the upper ²P_1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1601227

Journal Information:: Journal of Physical Chemistry Letters, Vol. 11, Issue 5; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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References (54)

Theory and applications of charge-transfer-to-solvent spectra Blandamer, Michael J.; Fox, Malcom F. Chemical Reviews, Vol. 70, Issue 1 https://doi.org/10.1021/cr60263a002	journal	February 1970
Electron Transfer Spectra and Their Photochemical Effects Rabinowitch, Eugene Reviews of Modern Physics, Vol. 14, Issue 2-3 https://doi.org/10.1103/RevModPhys.14.112	journal	April 1942
Solvation spectra. Part 1.—The effect of environmental changes upon the ultra-violet absorption of solvated iodide ions Smith, M.; Symons, M. C. R. Trans. Faraday Soc., Vol. 54, Issue 0 https://doi.org/10.1039/TF9585400338	journal	January 1958
The Relation Between Lyotropic and Spectroscopic Properties of Anions in Solution Meyerstein, Dan; Treinin, Avner The Journal of Physical Chemistry, Vol. 66, Issue 3 https://doi.org/10.1021/j100809a017	journal	March 1962
Electron-transfer spectra of anions in solution. Part 2.—Temperature dependence of electron-transfer spectra of anions in aqueous solution Stein, Gabriel; Treinin, Avner Trans. Faraday Soc., Vol. 55, Issue 0 https://doi.org/10.1039/TF9595501091	journal	January 1959
Solvent scale for charge-transfer-to-solvent spectra of anions Burak, Itamar; Treinin, Avner Transactions of the Faraday Society, Vol. 59 https://doi.org/10.1039/tf9635901490	journal	January 1963
Solvation spectra. Part 60.—Specific solvation of iodide ions Symons, Martyn C. R.; Jackson, Susan E. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0 https://doi.org/10.1039/f19797501919	journal	January 1979
Effect of pressure on the ultra-violet absorption spectra of iodide in non-aqueous solvents Blandamer, M. J.; Burdett, T. R. Journal of the Chemical Society, Faraday Transactions 2, Vol. 68 https://doi.org/10.1039/f29726800577	journal	January 1972
Ultraviolet charge-transfer-to-solvent spectroscopy of halide and hydroxide ions in subcritical and supercritical water Marin, Timothy W.; Janik, Ireneusz; Bartels, David M. Physical Chemistry Chemical Physics, Vol. 21, Issue 44 https://doi.org/10.1039/C9CP03805A	journal	January 2019
The Ultrafast Dynamics of Photodetachment Chen, Xiyi; Bradforth, Stephen E. Annual Review of Physical Chemistry, Vol. 59, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104702	journal	May 2008
FORMATION OF THE HYDRATED ELECTRON IN THE FLASH PHOTOLYSIS OF AQUEOUS SOLUTIONS ¹ Matheson, Max S.; Mulac, W. A.; Rabani, Joseph The Journal of Physical Chemistry, Vol. 67, Issue 12 https://doi.org/10.1021/j100806a027	journal	December 1963
The far u.-v. absorption spectrum of the iodide ion in aqueous solution Jortner, Joshua; Raz, Baruch; Stein, Gabriel Transactions of the Faraday Society, Vol. 56 https://doi.org/10.1039/tf9605601273	journal	January 1960
Far ultraviolet solution spectroscopy of the iodide ion Fox, Malcolm F.; Hayon, Elie Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0 https://doi.org/10.1039/f19777301003	journal	January 1977
New CTTS absoprtion bands of iodide in the far-ultraviolet region Fox, M. F.; Hayon, E. Chemical Physics Letters, Vol. 14, Issue 4 https://doi.org/10.1016/0009-2614(72)80234-3	journal	June 1972
Resolution of the far ultraviolet absorption bands of solvated iodide Barker, B. E.; Fox, Malcolm F.; Walton, A. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 72, Issue 0 https://doi.org/10.1039/f19767200344	journal	January 1976
The ejection distribution of solvated electrons generated by the one-photon photodetachment of aqueous I− and two-photon ionization of the solvent Kloepfer, J. A.; Vilchiz, V. H.; Lenchenkov, V. A. The Journal of Chemical Physics, Vol. 113, Issue 15 https://doi.org/10.1063/1.1309011	journal	October 2000
Map for the Relaxation Dynamics of Hot Photoelectrons Injected into Liquid Water via Anion Threshold Photodetachment and above Threshold Solvent Ionization Vilchiz, Victor H.; Kloepfer, Jeremiah A.; Germaine, Amy C. The Journal of Physical Chemistry A, Vol. 105, Issue 10 https://doi.org/10.1021/jp003974m	journal	March 2001
Electronic and Solvent Relaxation Dynamics of a Photoexcited Aqueous Halide Sheu, Wen-Shyan; Rossky, Peter J. The Journal of Physical Chemistry, Vol. 100, Issue 4 https://doi.org/10.1021/jp9513531	journal	January 1996
Absence of a Signature of Aqueous I(²P_1/2) after 200-nm Photodetachment of I^-(aq) Moskun, Amy C.; Bradforth, Stephen E.; Thøgersen, Jan The Journal of Physical Chemistry A, Vol. 110, Issue 38 https://doi.org/10.1021/jp053992+	journal	September 2006
Excited States of Iodide Anions in Water: A Comparison of the Electronic Structure in Clusters and in Bulk Solution Bradforth, Stephen E.; Jungwirth, Pavel The Journal of Physical Chemistry A, Vol. 106, Issue 7 https://doi.org/10.1021/jp013068p	journal	February 2002
How Does the Solvent Control Electron Transfer? Experimental and Theoretical Studies of the Simplest Charge Transfer Reaction Barthel, Erik R.; Martini, Ignacio B.; Schwartz, Benjamin J. The Journal of Physical Chemistry B, Vol. 105, Issue 49 https://doi.org/10.1021/jp011150e	journal	December 2001
Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface Nowakowski, Paweł J.; Woods, David A.; Verlet, Jan R. R. The Journal of Physical Chemistry Letters, Vol. 7, Issue 20 https://doi.org/10.1021/acs.jpclett.6b01985	journal	October 2016
Hydrated Electrons at the Water/Air Interface Sagar, D. M.; Bain, Colin. D.; Verlet, Jan R. R. Journal of the American Chemical Society, Vol. 132, Issue 20 https://doi.org/10.1021/ja101176r	journal	April 2010
Charge-transfer-to-solvent spectra of an aqueous halide revisited via computer simulation Sheu, Wen Shyan; Rossky, Peter J. Journal of the American Chemical Society, Vol. 115, Issue 17 https://doi.org/10.1021/ja00070a017	journal	August 1993
Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy Elles, Christopher G.; Rivera, Christopher A.; Zhang, Yuyuan The Journal of Chemical Physics, Vol. 130, Issue 8 https://doi.org/10.1063/1.3078336	journal	February 2009
Fundamentals of Sum-Frequency Spectroscopy Shen, Y. R. Cambridge University Press https://doi.org/10.1017/CBO9781316162613	book	February 2016
The free surface of water: molecular orientation, surface potential and nonlinear susceptibility Molecular Physics, Vol. 92, Issue 4 https://doi.org/10.1080/002689797169916	journal	November 1997
A Unified Treatment of Selection Rules and Symmetry Relations for Sum-Frequency and Second Harmonic Spectroscopies Moad, Andrew J.; Simpson, Garth J. The Journal of Physical Chemistry B, Vol. 108, Issue 11 https://doi.org/10.1021/jp035362i	journal	March 2004
Theoretical Formulation and Simulation of Electronic Sum-Frequency Generation Spectroscopy Lin, Chih-Kai; Hayashi, Michitoshi; Lin, Sheng Hsien The Journal of Physical Chemistry C, Vol. 117, Issue 45 https://doi.org/10.1021/jp407881a	journal	October 2013
On the Nature of ions at the Liquid Water Surface Petersen, Poul B.; Saykally, Richard J. Annual Review of Physical Chemistry, Vol. 57, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104609	journal	May 2006
Direct experimental validation of the Jones–Ray effect Petersen, Poul B.; Johnson, Justin C.; Knutsen, Kelly P. Chemical Physics Letters, Vol. 397, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.08.048	journal	October 2004
Broadband Deep UV Spectra of Interfacial Aqueous Iodide Rizzuto, Anthony M.; Irgen-Gioro, Shawn; Eftekhari-Bafrooei, Ali The Journal of Physical Chemistry Letters, Vol. 7, Issue 19 https://doi.org/10.1021/acs.jpclett.6b01931	journal	September 2016
Charge-Transfer-to-Solvent Spectrum of Thiocyanate at the Air/Water Interface Measured by Broadband Deep Ultraviolet Electronic Sum Frequency Generation Spectroscopy Mizuno, Hikaru; Rizzuto, Anthony M.; Saykally, Richard J. The Journal of Physical Chemistry Letters, Vol. 9, Issue 16 https://doi.org/10.1021/acs.jpclett.8b01966	journal	August 2018
Charge transfer to solvent dynamics in iodide aqueous solution studied at ionization threshold Kothe, Alexander; Wilke, Martin; Moguilevski, Alexandre Physical Chemistry Chemical Physics, Vol. 17, Issue 3 https://doi.org/10.1039/C4CP02482F	journal	January 2015
Real-time observation of the charge transfer to solvent dynamics Messina, Fabrizio; Bräm, Olivier; Cannizzo, Andrea Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3119	journal	July 2013
Flowing liquid sample jet for resonance Raman and ultrafast optical spectroscopy Tauber, Michael J.; Mathies, Richard A.; Chen, Xiyi Review of Scientific Instruments, Vol. 74, Issue 11 https://doi.org/10.1063/1.1614874	journal	November 2003
Electronic Structure of Liquid Methanol and Ethanol from Polarization-Dependent Two-Photon Absorption Spectroscopy Bhattacharyya, Dhritiman; Zhang, Yuyuan; Elles, Christopher G. The Journal of Physical Chemistry A, Vol. 123, Issue 27 https://doi.org/10.1021/acs.jpca.9b04040	journal	June 2019
Über Absorptionsspektren negativer Halogenionen in Lösung Franck, J.; Scheibe, G. Zeitschrift für Physikalische Chemie, Vol. 139A, Issue 1 https://doi.org/10.1515/zpch-1928-13904	journal	January 1928
On the Photochemistry of Aqueous Solutions of Chloride, Bromide, and Iodide Ions Jortner, Joshua; Ottolenghi, Michael; Stein, Gabriel The Journal of Physical Chemistry, Vol. 68, Issue 2 https://doi.org/10.1021/j100784a005	journal	February 1964
The role of the hydration configuration in electronic processes involving ions in aqueous solution Platzman, Robert; Franck, James Zeitschrift f�r Physik, Vol. 138, Issue 3-4 https://doi.org/10.1007/BF01340687	journal	June 1954
Intensities of the absorption bands of halide ions in solution Jortner, Joshua; Treinin, Avner Transactions of the Faraday Society, Vol. 58 https://doi.org/10.1039/tf9625801503	journal	January 1962
Three-Photon Excitation of Xenon and Carbon Monoxide Faisal, F. H. M.; Wallenstein, R.; Zacharias, H. Physical Review Letters, Vol. 39, Issue 18 https://doi.org/10.1103/PhysRevLett.39.1138	journal	October 1977
Collisional deactivation of Xe(5 p ⁵ 6 p ) states in Xe and Ar Ku, J. K.; Setser, D. W. The Journal of Chemical Physics, Vol. 84, Issue 8 https://doi.org/10.1063/1.450825	journal	April 1986
Solvation spectra. Part 5.—Effect of pressure on the ultra-violet absorption spectrum of solvated iodide Blandamer, M. J.; Gough, T. E.; Symons, M. C. R. Trans. Faraday Soc., Vol. 59, Issue 0 https://doi.org/10.1039/TF9635901748	journal	January 1963
Effects of cations upon absorption spectra. Part 5.—Charge-transfer-to-solvent spectrum of iodide and ion-pair formation Griffiths, T. R.; Wijayanayake, R. H. Trans. Faraday Soc., Vol. 66, Issue 0 https://doi.org/10.1039/TF9706601563	journal	January 1970
Two- and three-photon ionization in the noble gases McGuire, E. J. Physical Review A, Vol. 24, Issue 2 https://doi.org/10.1103/PhysRevA.24.835	journal	August 1981
Elucidating the mechanism of selective ion adsorption to the liquid water surface Otten, D. E.; Shaffer, P. R.; Geissler, P. L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 3 https://doi.org/10.1073/pnas.1116169109	journal	January 2012
Thermodynamics of iodide adsorption at the instantaneous air-water interface Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J. The Journal of Chemical Physics, Vol. 138, Issue 11 https://doi.org/10.1063/1.4794688	journal	March 2013
Atomistic simulation of ion solvation in water explains surface preference of halides Caleman, C.; Hub, J. S.; van Maaren, P. J. Proceedings of the National Academy of Sciences, Vol. 108, Issue 17 https://doi.org/10.1073/pnas.1017903108	journal	April 2011
Water-mediated ion-ion interactions are enhanced at the water vapor-liquid interface Venkateshwaran, V.; Vembanur, S.; Garde, S. Proceedings of the National Academy of Sciences, Vol. 111, Issue 24 https://doi.org/10.1073/pnas.1403294111	journal	June 2014
Intermolecular correlation effect in sum frequency generation spectroscopy of electrolyte aqueous solution Ishiyama, Tatsuya; Morita, Akihiro Chemical Physics Letters, Vol. 431, Issue 1-3 https://doi.org/10.1016/j.cplett.2006.09.024	journal	November 2006
Molecular Dynamics Study of Gas−Liquid Aqueous Sodium Halide Interfaces. I. Flexible and Polarizable Molecular Modeling and Interfacial Properties Ishiyama, Tatsuya; Morita, Akihiro The Journal of Physical Chemistry C, Vol. 111, Issue 2 https://doi.org/10.1021/jp065191s	journal	January 2007
Water in Hydration Shell of an Iodide Ion: Structure and Dynamics of Solute-Water Hydrogen Bonds and Vibrational Spectral Diffusion from First-Principles Simulations Karmakar, Anwesa; Chandra, Amalendu The Journal of Physical Chemistry B, Vol. 119, Issue 27 https://doi.org/10.1021/jp510714e	journal	June 2015
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996

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Interfaces
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Title: New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk

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