6533b822fe1ef96bd127d608

RESEARCH PRODUCT

Electron Energy Loss and DFT/SCI Study of the Singlet and Triplet Excited States of Aminobenzonitriles and Benzoquinuclidines:  Role of the Amino Group Twist Angle

Klaas A. ZachariasseStefan GrimmeNorbert DetzerChristophe BulliardGabriele WirtzEdwin HaselbachMichael Allan

subject

ChemistryExcited stateSinglet fissionMoleculeDensity functional theorySinglet statePhysical and Theoretical ChemistryTwistAtomic physicsSpectroscopyGround state

description

Spectroscopic consequences of varying the twist angle of the amino group in aminobenzonitrile systems in the electronic ground state are investigated by applying electron energy loss (EEL) spectroscopy and density functional theory to 4-N,N-dimethylaminobenzonitrile (DMABN), 4-N,N-dimethylamino-3,5-dimethylbenzonitrile (MMD), benzoquinuclidine (BQ), and 6-cyanobenzoquinuclidine (CBQ). A number of singlet and triplet excited states was observed and assigned with the help of DFT/SCI theory. The results characterize the gas-phase spectroscopy of the molecules and verify to within 0.3 eV the predictive power of DFT/SCI theory for vertical states over a wide range of twist and pyramidalization angles. The amino group configuration in the relaxed charge-transfer state of dual fluorescent aminobenzonitriles in solution cannot be directly deduced from the present data, however.

yearjournalcountryeditionlanguage
1999-09-01The Journal of Physical Chemistry A
https://doi.org/10.1021/jp990922s