Isotope effects of ground and lowest lying vibrational states of H3-xDxO2- complexes
Isotope effects of the H3O−23O2−<math display="inline" overflow="scroll" altimg="eq-00002.gif"><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub><msubsup><mrow><mi mathvariant="normal">O<...
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| Hauptverfasser: | , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
05 February 2016
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| In: |
The journal of chemical physics
Year: 2016, Jahrgang: 144, Heft: 5, Pages: 054308 |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4940965 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1063/1.4940965 Verlag, lizenzpflichtig, Volltext: https://aip.scitation.org/doi/10.1063/1.4940965 
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| Verfasserangaben: | Narjes Ansari, and Hans-Dieter Meyer |
| Zusammenfassung: | Isotope effects of the H3O−23O2−<math display="inline" overflow="scroll" altimg="eq-00002.gif"><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub><msubsup><mrow><mi mathvariant="normal">O</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math> anion are investigated. For this, the 24 lowest excited vibrational states of the H3−xDxO−23−xDxO2−<math display="inline" overflow="scroll" altimg="eq-00003.gif"><msub><mrow></mrow><mrow><mn>3</mn><mo>−</mo><mi mathvariant="normal">x</mi></mrow></msub><msub><mrow><mi mathvariant="normal">D</mi></mrow><mrow><mi mathvariant="normal">x</mi></mrow></msub><msubsup><mrow><mi mathvariant="normal">O</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math> complexes, with x = 0-3, are computed using two different Hamiltonians, namely, a 7D reduced-dimensionality one with a numerical representation of the kinetic energy operator (KEO) and a 9D full-dimensionality Hamiltonian with an exact analytic KEO. The computations are carried out with the multiconfiguration time-dependent Hartree method. The obtained results show that bridge and terminal H-D exchange cause a variation in energy with or without a rearrangement of states. A clear rearrangement of fundamental modes is observed in bridge H-D exchange of the H3O−23O2−<math display="inline" overflow="scroll" altimg="eq-00004.gif"><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub><msubsup><mrow><mi mathvariant="normal">O</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math> complex, where the frequency of bridge hydrogen stretching (z) is strongly lowered by substitution. The isotope effects show that rotation (ϕ), rocking (u1 + u2), wagging (u1 − u2), and O-O stretch (R) modes are sensitive to terminal H-D exchange, while the bridge-atom bending (x,y) and stretch (z) modes are sensitive to bridge H-D exchange. An influence coefficient, which measures the influence of an excitation of one mode on the various 1D reduced densities, is defined and analyzed in detail. It is shown that the D3O−23O2−<math display="inline" overflow="scroll" altimg="eq-00005.gif"><msub><mrow></mrow><mrow><mn>3</mn></mrow></msub><msubsup><mrow><mi mathvariant="normal">O</mi></mrow><mrow><mn>2</mn></mrow><mrow><mo>−</mo></mrow></msubsup></math> complex is more strongly correlated or coupled than the other isotopologues. |
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| Beschreibung: | Im Text ist das Zeichen "-" bei der Zahl "3" tiefgestellt Im Text ist das Zeichen "-" bei der Zahl "2" hochgestellt Im Text sind "3", "x" und "2" tiefgestellt Gesehen am 18.08.2020 |
| Beschreibung: | Online Resource |
| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4940965 |