Open AccessCooperative Effect of Hydrogen-Bonded Chains in the Environment of a π → π* Chromophore
Author(s) -
Georgios Fradelos,
Jakub W. Kamiński,
Tomasz A. Wesołowski,
Samuel Leutwyler
Publication year - 2009
Publication title -
the journal of physical chemistry a
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.756
H-Index - 235
eISSN - 1520-5215
pISSN - 1089-5639
DOI - 10.1021/jp906483z
Subject(s) - cooperativity , chromophore , molecule , ionization , chemistry , spectral line , chemical physics , coupling (piping) , computational chemistry , hydrogen , molecular physics , atomic physics , materials science , physics , photochemistry , ion , quantum mechanics , organic chemistry , biochemistry , metallurgy
Laser resonant two-photon ionization UV spectra provide clear evidence that the effect of increasing the length of the hydrogen-bonded chain consisting of molecules such as NH(3), H(2)O, or CH(3)OH on the pi --> pi* excitations of cis-7-hydroxyquinoline (cis-7HQ) is strongly cooperative [ Thut ; et al. J. Phys. Chem. A 2008 , 112 , 5566. ] A theoretical analysis of the experimental data is provided to identify the origin of this cooperativity for four chains. The computational method to determine the changes of the electronic structure of a molecule due to interactions with its environment uses the nonempirical expression for the embedding potential [ Wesolowski ; Warshel J. Phys. Chem. 1993 , 97 , 8050. ] It is concluded that the electronic coupling between the molecules at the ends of the chain, which are hydrogen-bonded to cis-7HQ, plays a crucial role in this cooperativity.
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