In this paper we consider a theory for intramolecular radiationless transitions in an isolated molecule. The Born–Oppenheimer zero‐order excited states are not pure in view of configuration interaction between nearly degenerate zero‐order states, leading to the broadening of the excited state, the line shape being Lorentzian. The optically excited state can be described in terms of a superposition of molecular eigenstates, and the resulting wavefunction exhibits an exponential nonradiative decay. The linewidth and the radiationless lifetime are expressed in terms of a single molecular parameter, that is the square of the interaction energy between the zero‐order state and the manifold of all vibronic states located within one energy unit around that state. The validity criteria for the occurrence of an unimolecular radiationless transition and for exponential decay in an isolated molecule are derived. Provided that the density of vibrational states is large enough (i.e., exceeds the reciprocal of the interaction matrix element) radiationless transitions are expected to take place. The gross effects of molecular structure on the relevant molecular parameters are discussed.
Skip Nav Destination
Article navigation
15 January 1968
Research Article|
September 05 2003
Intramolecular Radiationless Transitions
Mordechai Bixon;
Mordechai Bixon
Department of Chemistry, Tel‐Aviv University, Tel‐Aviv, Israel
Search for other works by this author on:
Joshua Jortner
Joshua Jortner
Department of Chemistry, Tel‐Aviv University, Tel‐Aviv, Israel
Search for other works by this author on:
J. Chem. Phys. 48, 715–726 (1968)
Article history
Received:
August 07 1967
Citation
Mordechai Bixon, Joshua Jortner; Intramolecular Radiationless Transitions. J. Chem. Phys. 15 January 1968; 48 (2): 715–726. https://doi.org/10.1063/1.1668703
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Could not validate captcha. Please try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00
Citing articles via
Related Content
Radiationless Transitions and Molecular Quantum Beats
J. Chem. Phys. (September 2003)
Effect of Temperature on Radiationless Transitions
J. Chem. Phys. (September 2003)
’’Proximity effect’’ in radiationless transitions
J. Chem. Phys. (August 2008)
Radiationless Transitions: A Semiclassical Model
J. Chem. Phys. (July 2004)
Radiationless transitions in linear polyenes
J. Chem. Phys. (September 1983)