ISSN:
0192-8651
Keywords:
ab initio
;
formimidol
;
H-bond
;
energy barrier
;
Chemistry
;
Theoretical, Physical and Computational Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
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
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
