Excimer formation in the mixed dimers of naphthalene and 1-methoxynaphthalene in a supersonic jet

A. Das, K. K. Mahato, T. Chakraborty

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Electronic spectra for the S1 ← S0 transition of jet-cooled mixed clusters of naphthalene and 1-methoxynaphthalene have been measured by laser-induced fluorescence excitation and dispersed fluorescence spectroscopy. Under jet-cooled conditions, naphthalene forms two isomeric 1 : 1 mixed dimers with 1-methoxynaphthalene, which exhibit significant differences in excimer formation dynamics from the locally excited states. One of the isomeric dimers emits excimer fluorescence when excited to the electronic origin of the lowest excited state but the other shows a significant barrier to formation of the excimer. The energy gap between the S1 states of naphthalene and 1-methoxynaphthalene is ∼ 350 cm-1. The observation of excimer emission, particularly when excited to the S1 origin of one of the isomeric dimers, supports our earlier proposal that for naphthalene-methoxynaphthalene mixed dimers energy exchange or exciton resonance interactions are not significant for the stabilization of the mixed excimers. The charge-transfer (CT) interaction and overlap between π-molecular orbitals of two molecules at a suitable geometry are considered to be the primary factors for the stability of the excimers. At higher naphthalene vapour pressure we have observed a mixed trimer of 2 : 1 composition of naphthalene and 1-methoxynaphthalene. The trimer does not emit excimer fluorescence when excited with additional vibrational energy in S1 up to 650 cm-1. The observation indicates that the geometry of the trimer is very different from the stack configuration essential for formation of the excimer.

Original languageEnglish
Pages (from-to)1813-1818
Number of pages6
JournalPhysical Chemistry Chemical Physics
Volume3
Issue number10
DOIs
Publication statusPublished - 08-08-2001

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excimers
naphthalene
Dimers
dimers
trimers
Fluorescence
Excited states
fluorescence
Geometry
Fluorescence spectroscopy
Molecular orbitals
excitation
Vapor pressure
1-methoxynaphthalene
Charge transfer
Energy gap
Stabilization
geometry
electronic spectra
laser induced fluorescence

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "Electronic spectra for the S1 ← S0 transition of jet-cooled mixed clusters of naphthalene and 1-methoxynaphthalene have been measured by laser-induced fluorescence excitation and dispersed fluorescence spectroscopy. Under jet-cooled conditions, naphthalene forms two isomeric 1 : 1 mixed dimers with 1-methoxynaphthalene, which exhibit significant differences in excimer formation dynamics from the locally excited states. One of the isomeric dimers emits excimer fluorescence when excited to the electronic origin of the lowest excited state but the other shows a significant barrier to formation of the excimer. The energy gap between the S1 states of naphthalene and 1-methoxynaphthalene is ∼ 350 cm-1. The observation of excimer emission, particularly when excited to the S1 origin of one of the isomeric dimers, supports our earlier proposal that for naphthalene-methoxynaphthalene mixed dimers energy exchange or exciton resonance interactions are not significant for the stabilization of the mixed excimers. The charge-transfer (CT) interaction and overlap between π-molecular orbitals of two molecules at a suitable geometry are considered to be the primary factors for the stability of the excimers. At higher naphthalene vapour pressure we have observed a mixed trimer of 2 : 1 composition of naphthalene and 1-methoxynaphthalene. The trimer does not emit excimer fluorescence when excited with additional vibrational energy in S1 up to 650 cm-1. The observation indicates that the geometry of the trimer is very different from the stack configuration essential for formation of the excimer.",
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Excimer formation in the mixed dimers of naphthalene and 1-methoxynaphthalene in a supersonic jet. / Das, A.; Mahato, K. K.; Chakraborty, T.

In: Physical Chemistry Chemical Physics, Vol. 3, No. 10, 08.08.2001, p. 1813-1818.

Research output: Contribution to journalArticle

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AB - Electronic spectra for the S1 ← S0 transition of jet-cooled mixed clusters of naphthalene and 1-methoxynaphthalene have been measured by laser-induced fluorescence excitation and dispersed fluorescence spectroscopy. Under jet-cooled conditions, naphthalene forms two isomeric 1 : 1 mixed dimers with 1-methoxynaphthalene, which exhibit significant differences in excimer formation dynamics from the locally excited states. One of the isomeric dimers emits excimer fluorescence when excited to the electronic origin of the lowest excited state but the other shows a significant barrier to formation of the excimer. The energy gap between the S1 states of naphthalene and 1-methoxynaphthalene is ∼ 350 cm-1. The observation of excimer emission, particularly when excited to the S1 origin of one of the isomeric dimers, supports our earlier proposal that for naphthalene-methoxynaphthalene mixed dimers energy exchange or exciton resonance interactions are not significant for the stabilization of the mixed excimers. The charge-transfer (CT) interaction and overlap between π-molecular orbitals of two molecules at a suitable geometry are considered to be the primary factors for the stability of the excimers. At higher naphthalene vapour pressure we have observed a mixed trimer of 2 : 1 composition of naphthalene and 1-methoxynaphthalene. The trimer does not emit excimer fluorescence when excited with additional vibrational energy in S1 up to 650 cm-1. The observation indicates that the geometry of the trimer is very different from the stack configuration essential for formation of the excimer.

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