TY - JOUR
T1 - Evidence for the need of a non-Born-Oppenheimer description of excited-state hydrogen transfer
AU - Sobolewski, Andrzej L.
AU - Domcke, Wolfgang
PY - 1993/8/6
Y1 - 1993/8/6
N2 - The HOCHCHCHNH (enol from) to OCHCHCHNH2 (keto form) excited-state isomerization of 1-amino-3-propenal is considered as a model system for photo-induced intramolecular hydrogen (or proton) transfer. The potential energy surfaces of the electronic ground state as well as of the lowest nπ* and ππ* excited singlet states have been characterized by ab initio compelte-active-space self-consistent-field and multireference configuration-interaction calculations. It is found that the nπ* potential energy function exhibits a significant barrier along the proton-transfer reaction coordinate, while the ππ* potential energy function is almost barrierless and intersects the nπ* surface, providing a pathway for ultrafast photo-induced proton transfer. It is argued that consideration of nπ*ππ* vibronic coupling is essential in understanding the photo-induced proton-transfer reaction.
AB - The HOCHCHCHNH (enol from) to OCHCHCHNH2 (keto form) excited-state isomerization of 1-amino-3-propenal is considered as a model system for photo-induced intramolecular hydrogen (or proton) transfer. The potential energy surfaces of the electronic ground state as well as of the lowest nπ* and ππ* excited singlet states have been characterized by ab initio compelte-active-space self-consistent-field and multireference configuration-interaction calculations. It is found that the nπ* potential energy function exhibits a significant barrier along the proton-transfer reaction coordinate, while the ππ* potential energy function is almost barrierless and intersects the nπ* surface, providing a pathway for ultrafast photo-induced proton transfer. It is argued that consideration of nπ*ππ* vibronic coupling is essential in understanding the photo-induced proton-transfer reaction.
UR - http://www.scopus.com/inward/record.url?scp=0002412660&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(93)80055-T
DO - 10.1016/0009-2614(93)80055-T
M3 - Article
AN - SCOPUS:0002412660
SN - 0009-2614
VL - 211
SP - 82
EP - 87
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1
ER -