標題: The dynamical correlation in spacer-mediated electron transfer couplings
作者: Yang, CH
Hsu, CP
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 28-Jun-2006
摘要: The dynamical correlation effect in electron transfer (ET) coupling was studied in this work, for cases where electrons tunnel through a many-electron environment. The ET couplings for three different bridge-mediated model systems were calculated: (I) trans-alkyl chains [H2C-(CH2)(n)-CH2, n=2-10], (II) two isomers of trans-1,4-dimethylenecyclohexane, and (III) two ethylenes spaced by a saturated ethane molecule. The couplings were calculated as half energy gaps of the two lowest adiabatic states. The dynamical correlation was included with spin-flip (SF) and ionization potential or electron affinity coupled-cluster singles and doubles (SF-CCSD and IP/EA-CCSD) and a Delta CCSD scheme. The direct coupling (DC) scheme is also used as a way to obtain a solution with nondynamical correlation, since DC uses approximated eigenstates that are symmetry-restoring linear combinations of two symmetry-broken unrestricted Hartree-Fock configurations. For all cases tested except for one, results from the DC scheme closely follow the CCSD data, indicating that the dual-configuration solutions can be a good approximation of wave functions with nondynamical correlation included, but there exist exceptions. Comparing the DC results with SF-CCSD and IP or EA-CCSD data, we concluded that the dynamical correlation effect is small for most of the cases we tested. (c) American Institute of Physics.
URI: http://dx.doi.org/10.1063/1.2207613
http://hdl.handle.net/11536/12126
ISSN: 0021-9606
DOI: 10.1063/1.2207613
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 124
Issue: 24
結束頁: 
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