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Title: Characterization of the primary hydration shell of the hydroxide ion with H 2 tagging vibrational spectroscopy of the OH - ∙ (H 2O) n=2,3 and OD - ∙ (D 2O) n=2,3 clusters

In this paper, we report the isotope-dependent vibrational predissociation spectra of the H 2-tagged OH - ∙ (H 2O) n=2,3 clusters, from which we determine the strongly coordination-dependent energies of the fundamentals due to the OH groups bound to the ion and the intramolecular bending modes of the water molecules. The HOH bending fundamental is completely missing in the delocalized OH - ∙ (H 2O) binary complex but is recovered upon adding the second water molecule, thereby establishing that the dihydrate behaves as a hydroxide ion solvated by two essentially intact water molecules. The energies of the observed OH stretches are in good agreement with the values predicted by Takahashi and co-workers [Phys. Chem. Chem. Phys. 17, 25505 (2015); 15, 114 (2013)] with a theoretical model that treats the strong anharmonicities at play in this system with explicit coupling between the bound OH groups and the O–O stretching modes on an extended potential energy surface. We highlight a surprising similarity between the spectral signatures of OH - ∙ (H 2O) 3 and the excess proton analogue, H 3O + ∙ (H 2O) 3, both of which correspond to completed hydration shells around the proton defect. Finally, we discuss the originmore » of the extreme solvatochromicity displayed by both OH - and H + in the context of the anomalously large “proton polarizabilities” of the H 5O 2 + and H 3O 2 - binary complexes.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [3] ; ORCiD logo [3] ;  [4] ; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  2. Univ. of the Virgin Islands, St. Thomas, VI (United States). College of Science and Mathematics
  3. Univ. of Pittsburgh, PA (United States). Dept. of Chemistry
  4. Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
Publication Date:
Grant/Contract Number:
FG02-06ER15066; FG02-00ER15066
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of Pittsburgh, PA (United States); Yale Univ., New Haven, CT (United States); Univ. of the Virgin Islands, St. Thomas, VI (United States); Univ. of Washington, Seattle, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; isotopic shift; isomerism; Doppler effect; chemical compounds and components; polarizability; chemical elements; correlation-consistent basis sets; vibrational spectra; potential energy surfaces; vibrational spectroscopy
OSTI Identifier:
1474097
Alternate Identifier(s):
OSTI ID: 1328508

Gorlova, Olga, DePalma, Joseph W., Wolke, Conrad T., Brathwaite, Antonio, Odbadrakh, Tuguldur T., Jordan, Kenneth D., McCoy, Anne B., and Johnson, Mark A.. Characterization of the primary hydration shell of the hydroxide ion with H2 tagging vibrational spectroscopy of the OH- ∙ (H2O)n=2,3 and OD- ∙ (D2O)n=2,3 clusters. United States: N. p., Web. doi:10.1063/1.4962912.
Gorlova, Olga, DePalma, Joseph W., Wolke, Conrad T., Brathwaite, Antonio, Odbadrakh, Tuguldur T., Jordan, Kenneth D., McCoy, Anne B., & Johnson, Mark A.. Characterization of the primary hydration shell of the hydroxide ion with H2 tagging vibrational spectroscopy of the OH- ∙ (H2O)n=2,3 and OD- ∙ (D2O)n=2,3 clusters. United States. doi:10.1063/1.4962912.
Gorlova, Olga, DePalma, Joseph W., Wolke, Conrad T., Brathwaite, Antonio, Odbadrakh, Tuguldur T., Jordan, Kenneth D., McCoy, Anne B., and Johnson, Mark A.. 2016. "Characterization of the primary hydration shell of the hydroxide ion with H2 tagging vibrational spectroscopy of the OH- ∙ (H2O)n=2,3 and OD- ∙ (D2O)n=2,3 clusters". United States. doi:10.1063/1.4962912. https://www.osti.gov/servlets/purl/1474097.
@article{osti_1474097,
title = {Characterization of the primary hydration shell of the hydroxide ion with H2 tagging vibrational spectroscopy of the OH- ∙ (H2O)n=2,3 and OD- ∙ (D2O)n=2,3 clusters},
author = {Gorlova, Olga and DePalma, Joseph W. and Wolke, Conrad T. and Brathwaite, Antonio and Odbadrakh, Tuguldur T. and Jordan, Kenneth D. and McCoy, Anne B. and Johnson, Mark A.},
abstractNote = {In this paper, we report the isotope-dependent vibrational predissociation spectra of the H2-tagged OH- ∙ (H2O)n=2,3 clusters, from which we determine the strongly coordination-dependent energies of the fundamentals due to the OH groups bound to the ion and the intramolecular bending modes of the water molecules. The HOH bending fundamental is completely missing in the delocalized OH- ∙ (H2O) binary complex but is recovered upon adding the second water molecule, thereby establishing that the dihydrate behaves as a hydroxide ion solvated by two essentially intact water molecules. The energies of the observed OH stretches are in good agreement with the values predicted by Takahashi and co-workers [Phys. Chem. Chem. Phys. 17, 25505 (2015); 15, 114 (2013)] with a theoretical model that treats the strong anharmonicities at play in this system with explicit coupling between the bound OH groups and the O–O stretching modes on an extended potential energy surface. We highlight a surprising similarity between the spectral signatures of OH- ∙ (H2O)3 and the excess proton analogue, H3O+ ∙ (H2O)3, both of which correspond to completed hydration shells around the proton defect. Finally, we discuss the origin of the extreme solvatochromicity displayed by both OH- and H+ in the context of the anomalously large “proton polarizabilities” of the H5O2+ and H3O2- binary complexes.},
doi = {10.1063/1.4962912},
journal = {Journal of Chemical Physics},
number = 13,
volume = 145,
place = {United States},
year = {2016},
month = {10}
}