Possible photoinduced spin transitions in bis(phenylmethylenyl)[2.2]paracyclophanes. A spin-orbit coupling study

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Abstract

A possible mechanism for the spin transitions in various stacking conformations of bis(phenylmethylenyl)[2.2]paracyclophanes, which have close-lying lowest singlet, triplet, and quintet spin states, is theoretically investigated by using diphenylcarbene dimers as models. Spin-orbit coupling (SOC) matrix elements, which play an essential role in the spin transition phenomena, are calculated with the effective one-electron spin-orbit Hamiltonian. The SOC between the first excited singlet state and the first excited triplet state and that between the first excited triplet state and the lowest quintet state are strong. The SOC between the first excited quintet state and the first excited triplet state and that between the first excited triplet state and the lowest singlet state are also strong. These results demonstrate that the spin conversion between the low-spin singlet state and the high-spin quintet state can occur via the first excited intermediate-spin triplet state. We propose that possible photoinduced spin-crossover phenomena can be observed in these organic molecular systems.

Original languageEnglish
Pages (from-to)7915-7920
Number of pages6
JournalJournal of Physical Chemistry A
Volume106
Issue number34
DOIs
Publication statusPublished - Aug 29 2002

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Excited states
Orbits
orbits
atomic energy levels
Hamiltonians
Dimers
Conformations
(2.2)paracyclophane
Electrons
electron spin
excitation
crossovers
dimers

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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title = "Possible photoinduced spin transitions in bis(phenylmethylenyl)[2.2]paracyclophanes. A spin-orbit coupling study",
abstract = "A possible mechanism for the spin transitions in various stacking conformations of bis(phenylmethylenyl)[2.2]paracyclophanes, which have close-lying lowest singlet, triplet, and quintet spin states, is theoretically investigated by using diphenylcarbene dimers as models. Spin-orbit coupling (SOC) matrix elements, which play an essential role in the spin transition phenomena, are calculated with the effective one-electron spin-orbit Hamiltonian. The SOC between the first excited singlet state and the first excited triplet state and that between the first excited triplet state and the lowest quintet state are strong. The SOC between the first excited quintet state and the first excited triplet state and that between the first excited triplet state and the lowest singlet state are also strong. These results demonstrate that the spin conversion between the low-spin singlet state and the high-spin quintet state can occur via the first excited intermediate-spin triplet state. We propose that possible photoinduced spin-crossover phenomena can be observed in these organic molecular systems.",
author = "Masakazu Kondo and Yoshihito Shiota and Kazunari Yoshizawa",
year = "2002",
month = "8",
day = "29",
doi = "10.1021/jp020984+",
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journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "ACS Publications",
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TY - JOUR

T1 - Possible photoinduced spin transitions in bis(phenylmethylenyl)[2.2]paracyclophanes. A spin-orbit coupling study

AU - Kondo, Masakazu

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

PY - 2002/8/29

Y1 - 2002/8/29

N2 - A possible mechanism for the spin transitions in various stacking conformations of bis(phenylmethylenyl)[2.2]paracyclophanes, which have close-lying lowest singlet, triplet, and quintet spin states, is theoretically investigated by using diphenylcarbene dimers as models. Spin-orbit coupling (SOC) matrix elements, which play an essential role in the spin transition phenomena, are calculated with the effective one-electron spin-orbit Hamiltonian. The SOC between the first excited singlet state and the first excited triplet state and that between the first excited triplet state and the lowest quintet state are strong. The SOC between the first excited quintet state and the first excited triplet state and that between the first excited triplet state and the lowest singlet state are also strong. These results demonstrate that the spin conversion between the low-spin singlet state and the high-spin quintet state can occur via the first excited intermediate-spin triplet state. We propose that possible photoinduced spin-crossover phenomena can be observed in these organic molecular systems.

AB - A possible mechanism for the spin transitions in various stacking conformations of bis(phenylmethylenyl)[2.2]paracyclophanes, which have close-lying lowest singlet, triplet, and quintet spin states, is theoretically investigated by using diphenylcarbene dimers as models. Spin-orbit coupling (SOC) matrix elements, which play an essential role in the spin transition phenomena, are calculated with the effective one-electron spin-orbit Hamiltonian. The SOC between the first excited singlet state and the first excited triplet state and that between the first excited triplet state and the lowest quintet state are strong. The SOC between the first excited quintet state and the first excited triplet state and that between the first excited triplet state and the lowest singlet state are also strong. These results demonstrate that the spin conversion between the low-spin singlet state and the high-spin quintet state can occur via the first excited intermediate-spin triplet state. We propose that possible photoinduced spin-crossover phenomena can be observed in these organic molecular systems.

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