The electronic quasicontinuum

M. Bixon, Joshua Jortner*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations


High n (=50-250) molecular Rydberg states are characterized by a high density (ρ ∝ n3/2Ry) of electronic states and by unique intramolecular couplings (V) which involve long-range Rydberg electron-core multipole interactions. We explore spectroscopic and dynamic implications of the dipole coupling V = CD(nn′)-3/2 of a doorway Rydberg state |n,l,N+,N〉 with a dense |{n′,l′,N+-1,N〉} manifold (n′ > n) of bound Rydberg states, which are described by Hund coupling case (d). We establish the conditions for the realization of the statistical limit (Vρ ≫ 1 and γρ > 1) and of the sparse mixed level structure (Vρ ≫ 1 and γρ < 1) within the mixed electronic manifold (where γ = Γ0/n3 are the nonradiative decay widths). The statistical limit for an electronic quasicontinuum is realized for the coupling strength domain 1.109Ry(B/Ry)3/8 < CD < (Γ0Ry/π)1/2, establishing how the characteristics of the level structure and dynamics are determined by the rotational constant B, by the molecular dipole moment (CD ∝ μ), by the decay width constant Γ0, and by l (where CD ∝ l-7). The statistical limit within an electronic quasicontinuum is expected to be amenable for experimental observation in polar large molecules, while the np(N+=0)-n′d(N+=1) coupling in H2O (Gilbert, R. D.; Child, M. S. Chem. Phys. Lett. 1991, 187, 153) corresponds to the sparse mixed level structure. Our analysis provides a generalization and unification of the theory of intramolecular coupling and dynamics for an electronic quasicontinuum.

Original languageEnglish
Pages (from-to)11914-11919
Number of pages6
JournalJournal of Physical Chemistry
Issue number29
StatePublished - 18 Jul 1996


Dive into the research topics of 'The electronic quasicontinuum'. Together they form a unique fingerprint.

Cite this