Ultrafast Dynamics of the Excited Mesitylene·Br-Atom EDA Complex

Jarzȩba, Włodzimierz; Hörmann, A.; Thakur, Khalid A. M.; Barbara, Paul F.

doi:10.1007/978-3-642-85176-6_200

Cited by 1 publication

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“…20 The applications reported here involve et processes occurring in the Zn 2 ͑H 2 O͒ ϩ system 18͑a͒ and the benzene-chlorine atom contact ion-pair system. 21 The calculated results for these systems, which are dominated by direct ͓or ''through-space'' ͑TS͒ 1,7 ͔ D/A coupling, allow critical comparisons of the GMH and BD methods. 22 We find that the two methods yield quite similar results and that either is a robust, general means for calculating H ab for ground or excited state et processes.…”

Section: Introductionmentioning

confidence: 99%

Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: Comparison of the generalized Mulliken–Hush and block diagonalization methods

Cave

Newton

1997

The Journal of Chemical Physics

454

339

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Two independent methods are presented for the nonperturbative calculation of the electronic coupling matrix element (H ab) for electron transfer reactions using ab initio electronic structure theory. The first is based on the generalized Mulliken-Hush ͑GMH͒ model, a multistate generalization of the Mulliken Hush formalism for the electronic coupling. The second is based on the block diagonalization ͑BD͒ approach of Cederbaum, Domcke, and co-workers. Detailed quantitative comparisons of the two methods are carried out based on results for ͑a͒ several states of the system Zn 2 OH 2 ϩ and ͑b͒ the low-lying states of the benzene-Cl atom complex and its contact ion pair. Generally good agreement between the two methods is obtained over a range of geometries. Either method can be applied at an arbitrary nuclear geometry and, as a result, may be used to test the validity of the Condon approximation. Examples of nonmonotonic behavior of the electronic coupling as a function of nuclear coordinates are observed for Zn 2 OH 2 ϩ. Both methods also yield a natural definition of the effective distance (r DA) between donor (D) and acceptor (A) sites, in contrast to earlier approaches which required independent estimates of r DA , generally based on molecular structure data.

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Section: Introductionmentioning

confidence: 99%