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

研究成果: 雜誌貢獻期刊論文同行評審

11 引文 斯高帕斯(Scopus)

摘要

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.

原文英語
頁(從 - 到)10478-10482
頁數5
期刊Journal of Physical Chemistry A
111
發行號42
DOIs
出版狀態已發佈 - 2007 十月 25

ASJC Scopus subject areas

  • 物理與理論化學

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