Signature OH absorption spectrum from cluster models of solvation: A solvent-to-solute charge transfer state

Ming Kang Tsai, Karol Kowalski, Marat Valiev, Michel Dupuis

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Ab initio electronic structure theory calculations on cluster models support the characterization of the signature absorption spectrum of a solvated hydroxyl OH radical as a solvent-to-solute charge transfer state modulated by the hydrogen-bonding environment. Vertical excited states in OH(H 2O) n clusters (n = 0-7, 16) calculated at the TDDFT level of theory (with companion calculations at the EOM-CCSD level of theory for n ≤ 7) show an intense band in the region of ∼250 nm. The calculations suggest that the intensity of the solventto-solute charge transfer transition depends strongly on a favorable alignment of the donor and acceptor molecular orbitais, as observed in one (n = 16) cluster, In the other (smaller) clusters, the transitions in this region were found to be weak as the clusters do not offer the necessary favorable alignment of orbitais. The present findings are consistent with the experimentally observed absorption at 230 nm that has been assigned to a solvent-to-solute charge transfer and provide insight into the electronic states and orbitais that give rise to the intensity of the band.

Original languageEnglish
Pages (from-to)10478-10482
Number of pages5
JournalJournal of Physical Chemistry A
Volume111
Issue number42
DOIs
Publication statusPublished - Oct 25 2007

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Solvation
solvation
Charge transfer
Absorption spectra
solutes
charge transfer
signatures
absorption spectra
Electronic states
Excited states
Hydroxyl Radical
Electronic structure
alignment
Hydrogen bonds
electronic structure
hydrogen
electronics
excitation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Signature OH absorption spectrum from cluster models of solvation : A solvent-to-solute charge transfer state. / Tsai, Ming Kang; Kowalski, Karol; Valiev, Marat; Dupuis, Michel.

In: Journal of Physical Chemistry A, Vol. 111, No. 42, 25.10.2007, p. 10478-10482.

Research output: Contribution to journalArticle

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AB - Ab initio electronic structure theory calculations on cluster models support the characterization of the signature absorption spectrum of a solvated hydroxyl OH radical as a solvent-to-solute charge transfer state modulated by the hydrogen-bonding environment. Vertical excited states in OH(H 2O) n clusters (n = 0-7, 16) calculated at the TDDFT level of theory (with companion calculations at the EOM-CCSD level of theory for n ≤ 7) show an intense band in the region of ∼250 nm. The calculations suggest that the intensity of the solventto-solute charge transfer transition depends strongly on a favorable alignment of the donor and acceptor molecular orbitais, as observed in one (n = 16) cluster, In the other (smaller) clusters, the transitions in this region were found to be weak as the clusters do not offer the necessary favorable alignment of orbitais. The present findings are consistent with the experimentally observed absorption at 230 nm that has been assigned to a solvent-to-solute charge transfer and provide insight into the electronic states and orbitais that give rise to the intensity of the band.

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