Title

Proton Transfer in the Ground and First Excited Triplet States of Malonaldehyde

Document Type

Article

Journal/Book Title

Journal of Physical Chemistry

Publication Date

1992

Publisher

American Chemical Society

Volume

96

Issue

24

First Page

9764

Last Page

9767

DOI

10.1021/j100203a035

Abstract

The intramolecular proton-transfer process in malonaldehyde is studied by ab initio methods in its ground electronic state and in its excited r - r* triplet state. The transfer barrier is considerably higher in T1, which is attributed in part to the virtual disappearance of the hydrogen-bonding interaction present in the ground state. The weakening of this H bond in the excited state is associated with a less acidic protondonor OH group and less basic acceptor oxygen. The r - r* excitation adds antibonding character to the C=O bond. which causes it to elongate. The ensuing reduction in its bond dipole help to weaken the intramolecular H bond.

Comments

Originally published by American Chemical Society in the Journal of Physical Chemistry.

Publisher's PDF can be accessed through the remote link. May require fee or subscription.

Share

COinS