Name
Title | ||
|---|---|---|
Effect of nonproximate atomic substitution on excited state intramolecular proton transfer |
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 --> pi(*) excitation in both molecules, which is accompanied by a heightened barrier to proton transfer.(3) pi pi(*) behaves in the same manner, but the singlet pi pi(*) 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 --> pi(*) excitation upon the H-bond and increases the excitation energies of the various states, particularly pi pi(*). (C) 1998 John Wiley & Sons, Inc. |
Year | DOI | Venue |
|---|---|---|
1998 | 10.1002/(SICI)1096-987X(19980130)19:2<129::AID-JCC5>3.0.CO;2-W | JOURNAL OF COMPUTATIONAL CHEMISTRY |
Keywords | Field | DocType |
ab initio,formimidol,H-bond,energy barrier | Excited state,Proton,Intramolecular force,Ab initio quantum chemistry methods,Ground state,Atomic physics,Computational chemistry,Chemistry,Atom,Singlet state,Ab initio | Journal |
Volume | Issue | ISSN |
19 | 2 | 0192-8651 |
Citations | PageRank | References |
0 | 0.34 | 0 |
Authors | ||
3 | ||
Name | Order | Citations | PageRank |
|---|---|---|---|
| Martin Cuma | 1 | 16 | 2.28 |
| Clifton Thompson | 2 | 0 | 0.34 |
| Steve Scheiner | 3 | 4 | 2.67 |