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Title: Na+ affinity of a series of substituted acetophenones in their low-lying excited triplet state: A DFT based computational study
Authors: Senapati, U
De, D
De, B R
Keywords: Theoretical chemistry;Density functional calculations;Gas phase ion chemistry;Charge distribution;Acetophenones
Issue Date: 11-Dec-2014
Abstract: A detailed study of Na+ affinities of a series of para-substituted acetophenones and their O–Na+ counterparts has been carried out using density functional theory by B3LYP method using 6-311G(d,p) basis set with complete geometry optimization in the relevant excited state. The gas phase O–Na+ complex formation is exothermic and the local stereochemical disposition of the Na+ is found to be almost the same in each case. The presence of para-substituent causes very little change in the Na+ affinity relative to the unsubstituted acetophenones. Electron releasing p-substituents are seen to increase the affinity, while electron withdrawing p-substituents have an opposite effect. The computed Na+ affinities are correlated with a number of computed system parameters such as the net charge on the Na+ and the carbonyl oxygen of the Na+ complexes and the net charge on the carbonyl oxygen of the free bases as well as the computed hardness of the free bases. The Na+ ion induced shifts are, in general, red shifts for the low-lying excited triplet state. The energetics, structural and electronic properties of the complexes indicate that in the lowest excited triplet state the interaction between the Na+ ion and a carbonyl base is predominantly an ion-dipole attraction and the ion-induced dipole interaction as well rather than a covalent interaction.
Page(s): 1526-1530
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.53A(12) [December 2014]

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