A three-state effective Hamiltonian for symmetric cationic diarylmethanes

Olsen, Seth and McKenzie, Ross H. (2012) A three-state effective Hamiltonian for symmetric cationic diarylmethanes. Journal of Chemical Physics, 136 23: . doi:10.1063/1.4728158


Author Olsen, Seth
McKenzie, Ross H.
Title A three-state effective Hamiltonian for symmetric cationic diarylmethanes
Journal name Journal of Chemical Physics   Check publisher's open access policy
ISSN 0021-9606
1089-7690
Publication date 2012-06-21
Sub-type Article (original research)
DOI 10.1063/1.4728158
Volume 136
Issue 23
Total pages 11
Place of publication College Park, MD, United States
Publisher American Institute of Physics
Collection year 2013
Language eng
Abstract We analyze the low-energy electronic structure of a series of symmetric cationic diarylmethanes, which are bridge-substituted derivatives of Michler’s Hydrol Blue. We use a four-electron, threeorbital complete active space self-consistent field and multi-state multi-reference perturbation theory model to calculate a three-state diabatic effective Hamiltonian for each dye in the series. We exploit an isolobal analogy between the active spaces of the self-consistent field solutions for each dye to represent the electronic structure in a set of analogous diabatic states. The diabatic states can be identified with the bonding structures in classical resonance-theoretic models of cyanine dyes. We identify diabatic states with opposing charge and bond-order localization, analogous to the classical resonance structures, and a third state with charge on the bridge. While the left- and right-charged structures are similar for all dyes, the structure of the bridge-charged diabatic state, and the Hamiltonian matrix elements connected to it, change significantly across the series. The change is correlated with an inversion of the sign of the charge carrier on the bridge, which changes from an electron pair to a hole as the series is traversed.
Keyword Nonlinear optical properties
Fluorescence up-conversion
Configuration interaction
Substituent constants
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ
Additional Notes Article # 234313

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Mathematics and Physics
Official 2013 Collection
 
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