Title

Effect of Nonproximate Atomic Substitution on Excited State Intramolecular Proton Transfer

Document Type

Article

Journal/Book Title

Journal of Computational Chemistry

Publication Date

12-1998

Publisher

Wiley-Blackwell

Volume

19

Issue

2

First Page

129

Last Page

138

DOI

10.1002/(SICI)1096-987X(19980130)19:2<129::AID-JCC5>3.0.CO;2-W

Abstract

The central C atom of the OCCCO skeleton of the malonaldehyde molecule is replaced by N, and the effects upon the intramolecular H-bond and the proton transfer are monitored by ab initio calculations in the ground and excited electronic states. The H-bond is weakened in the singlet and triplet states arising from n→π* excitation in both molecules, which is accompanied by a heightened barrier to proton transfer.3ππ* behaves in the same manner, but the singlet ππ* state has a stronger H-bond and lower barrier. Replacement of the central C atom by N strengthens the intramolecular H-bond. Although the proton transfer barrier in the ground state of formimidol is lower than in malonaldehyde, the barriers in all four excited states are higher in the N-analog. The latter substitution also dampens the effect of the n→π* excitation upon the H-bond and increases the excitation energies of the various states, particularly ππ*. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 129–138, 1998

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