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Iodide solvation in tetrahydrofuran clusters: I (THF) n (1 ≤  n  ≤ 30).

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Title: Iodide solvation in tetrahydrofuran clusters: I (THF) n (1 ≤  n  ≤ 30).
Authors: Young, Ryan M.1, Azar, R. Julian1,2, Yandell, Margaret A.1, King, Sarah B.1, Head-Gordon, Martin1,2, Neumark, Daniel M.1,2 dneumark@berkeley.edu
Source: Molecular Physics. 8/10/2012, Vol. 110 Issue 15/16, p1787-1799. 13p. 1 Diagram, 2 Charts, 10 Graphs.
Subjects: Iodides, Solvation, Tetrahydrofuran, Molecular orbitals, Chemical decomposition, Electrostatics, Molecular structure, Microclusters
Abstract: The solvent structure and binding motif of iodide-doped tetrahydrofuran clusters, I−(THF) n (1 ≤ n ≤ 30) are investigated with anion photoelectron imaging, molecular dynamics simulations, and ab initio calculations of vertical detachment energies. Experimentally, a dramatic decrease in the iodide differential stabilization energy and concomitant change in the mass spectrum at n = 9 suggest that the first solvation shell closes at n = 9–10 THF molecules, in rough agreement with the theoretical result of n = 7–9 determined from the computation of relaxed and unrelaxed solvent distribution densities. Analysis of the vertical detachment energy vs. inverse cluster radius suggests the iodide atom is maximally coordinated around n = 9. Decomposition of the interaction energies of I−(THF), its vertically-detached complement, and the (THF)2 dimer, employing the absolutely-localized molecular orbital energy decomposition analysis (ALMO EDA) scheme, highlights the dependence of electron binding and detachment on both electrostatics and polarization, with direct evidence of the fundamental importance of polarizability to a description of detachment. Experimental and theoretical evidence for an anionic electronically excited state is also presented; computed excitation energies and their attendant characters are discussed. The results are interpreted within the framework of the inefficient packing that occurs in bulk neat THF. [ABSTRACT FROM AUTHOR]
Copyright of Molecular Physics is the property of Taylor & Francis Ltd and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
Database: Engineering Source
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Header DbId: egs
DbLabel: Engineering Source
An: 78935957
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PubType: Academic Journal
PubTypeId: academicJournal
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  Data: Iodide solvation in tetrahydrofuran clusters: I (THF) n (1 ≤  n  ≤ 30).
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  Data: <searchLink fieldCode="AR" term="%22Young%2C+Ryan+M%2E%22">Young, Ryan M.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Azar%2C+R%2E+Julian%22">Azar, R. Julian</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Yandell%2C+Margaret+A%2E%22">Yandell, Margaret A.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22King%2C+Sarah+B%2E%22">King, Sarah B.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Head-Gordon%2C+Martin%22">Head-Gordon, Martin</searchLink><relatesTo>1,2</relatesTo><br /><searchLink fieldCode="AR" term="%22Neumark%2C+Daniel+M%2E%22">Neumark, Daniel M.</searchLink><relatesTo>1,2</relatesTo><i> dneumark@berkeley.edu</i>
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  Data: <searchLink fieldCode="JN" term="%22Molecular+Physics%22">Molecular Physics</searchLink>. 8/10/2012, Vol. 110 Issue 15/16, p1787-1799. 13p. 1 Diagram, 2 Charts, 10 Graphs.
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  Data: <searchLink fieldCode="DE" term="%22Iodides%22">Iodides</searchLink><br /><searchLink fieldCode="DE" term="%22Solvation%22">Solvation</searchLink><br /><searchLink fieldCode="DE" term="%22Tetrahydrofuran%22">Tetrahydrofuran</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+orbitals%22">Molecular orbitals</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+decomposition%22">Chemical decomposition</searchLink><br /><searchLink fieldCode="DE" term="%22Electrostatics%22">Electrostatics</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+structure%22">Molecular structure</searchLink><br /><searchLink fieldCode="DE" term="%22Microclusters%22">Microclusters</searchLink>
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  Data: The solvent structure and binding motif of iodide-doped tetrahydrofuran clusters, I−(THF) n (1 ≤ n ≤ 30) are investigated with anion photoelectron imaging, molecular dynamics simulations, and ab initio calculations of vertical detachment energies. Experimentally, a dramatic decrease in the iodide differential stabilization energy and concomitant change in the mass spectrum at n = 9 suggest that the first solvation shell closes at n = 9–10 THF molecules, in rough agreement with the theoretical result of n = 7–9 determined from the computation of relaxed and unrelaxed solvent distribution densities. Analysis of the vertical detachment energy vs. inverse cluster radius suggests the iodide atom is maximally coordinated around n = 9. Decomposition of the interaction energies of I−(THF), its vertically-detached complement, and the (THF)2 dimer, employing the absolutely-localized molecular orbital energy decomposition analysis (ALMO EDA) scheme, highlights the dependence of electron binding and detachment on both electrostatics and polarization, with direct evidence of the fundamental importance of polarizability to a description of detachment. Experimental and theoretical evidence for an anionic electronically excited state is also presented; computed excitation energies and their attendant characters are discussed. The results are interpreted within the framework of the inefficient packing that occurs in bulk neat THF. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Molecular Physics is the property of Taylor & Francis Ltd and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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      – Type: doi
        Value: 10.1080/00268976.2012.679637
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      – Code: eng
        Text: English
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      Pagination:
        PageCount: 13
        StartPage: 1787
    Subjects:
      – SubjectFull: Iodides
        Type: general
      – SubjectFull: Solvation
        Type: general
      – SubjectFull: Tetrahydrofuran
        Type: general
      – SubjectFull: Molecular orbitals
        Type: general
      – SubjectFull: Chemical decomposition
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      – SubjectFull: Electrostatics
        Type: general
      – SubjectFull: Molecular structure
        Type: general
      – SubjectFull: Microclusters
        Type: general
    Titles:
      – TitleFull: Iodide solvation in tetrahydrofuran clusters: I (THF) n (1 ≤  n  ≤ 30).
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              Text: 8/10/2012
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              Y: 2012
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