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A Theoretical Investigation of Charge Transfer in Several Substituted Acridinium Ions

Lappe, Jason; Cave, Robert J; Newton, Marshall D; Rostov, Ivan

Description

We present calculations for various properties of the ground and excited states of several arylamine-substituted acridinium ion systems that have been studied experimentally. Using ab initio and semiempirical quantum mechanical methods together with the generalized Mulliken-Hush (GMH) model, we examine the excitation energies, dipole moment shifts, and electronic coupling elements for the vertical charge shift (CSh) processes in these systems. We also examine solvent effects on these properties...[Show more]

dc.contributor.authorLappe, Jason
dc.contributor.authorCave, Robert J
dc.contributor.authorNewton, Marshall D
dc.contributor.authorRostov, Ivan
dc.date.accessioned2015-12-13T22:58:16Z
dc.identifier.issn1520-6106
dc.identifier.urihttp://hdl.handle.net/1885/83391
dc.description.abstractWe present calculations for various properties of the ground and excited states of several arylamine-substituted acridinium ion systems that have been studied experimentally. Using ab initio and semiempirical quantum mechanical methods together with the generalized Mulliken-Hush (GMH) model, we examine the excitation energies, dipole moment shifts, and electronic coupling elements for the vertical charge shift (CSh) processes in these systems. We also examine solvent effects on these properties using a dielectric continuum reaction field model. The results are in generally good agreement with available experimental results and indicate that there is strong electronic coupling in these systems over a wide range of torsional angles. Nevetheless, the initial and final cationic states remain reasonably well-localized over this range, and thus TICT state formation is unlikely in these systems. Finally, a version of the GMH model based on Koopmans' Theorem is developed and found to yield coupling elements generally within a factor of 2 of the many-electron GMH for a sample acridinium system, but with overestimated adiabatic and diabatic dipole moment differences.
dc.publisherAmerican Chemical Society
dc.sourceJournal of Physical Chemistry B
dc.subjectKeywords: Charge shift (CSh); Dipole moment shifts; Electronic coupling elements; Photoexcitation; Absorption; Aromatic compounds; Electron transitions; Ground state; Molecular orientation; Organic solvents; Quantum theory; Charge transfer
dc.titleA Theoretical Investigation of Charge Transfer in Several Substituted Acridinium Ions
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
local.identifier.citationvolume109
dc.date.issued2005
local.identifier.absfor030799 - Theoretical and Computational Chemistry not elsewhere classified
local.identifier.ariespublicationMigratedxPub11647
local.type.statusPublished Version
local.contributor.affiliationLappe, Jason, Harvey Mudd College
local.contributor.affiliationCave, Robert J, Harvey Mudd College
local.contributor.affiliationNewton, Marshall D, Brookhaven National Laboratory
local.contributor.affiliationRostov, Ivan, Administrative Division, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.startpage6610
local.bibliographicCitation.lastpage6619
local.identifier.doi10.1021/jp0456133
dc.date.updated2015-12-12T07:22:00Z
local.identifier.scopusID2-s2.0-17544377435
CollectionsANU Research Publications

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