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Volumn 14, Issue 8, 2010, Pages 689-700

The role of the metal ion in the photophysical behavior of Co(II), Ni(II), and Cu(II) octabutoxynaphthalocyanines: Insights from ultra-fast time-resolved spectroscopy and DFT/TDDFT calculations

Author keywords

metallonaphthalocyanines; photophysics; TDDFT; ultra fast spectroscopy

Indexed keywords


EID: 78149430659     PISSN: 10884246     EISSN: None     Source Type: Journal    
DOI: 10.1142/S1088424610002598     Document Type: Conference Paper
Times cited : (4)

References (43)
  • 14
    • 85037090797 scopus 로고    scopus 로고
    • The classification of the (π,π*) excited states in terms of "singdoublets" and "tripdoublets" was originally introduced by Gouterman and co-workers [15]. Interaction between the 1(π,π*) states of the macrocycle and the unpaired d electron on the metal results in doublet states (singdoublets) while interaction between the 3(π,π*) states of the macrocycle and the unpaired d electron results into doublets (tripdoublets) and quartets
    • The classification of the (π,π*) excited states in terms of "singdoublets" and "tripdoublets" was originally introduced by Gouterman and co-workers [15]. Interaction between the 1(π,π*) states of the macrocycle and the unpaired d electron on the metal results in doublet states (singdoublets) while interaction between the 3(π,π*) states of the macrocycle and the unpaired d electron results into doublets (tripdoublets) and quartets.
  • 20
    • 85037108636 scopus 로고    scopus 로고
    • note
    • All calculations were performed with the ADF program package [21, 22]. Geometry optimizations and ground-state electronic structure calculations were performed using the local density approximation (LDA) functional of Vosko-Wilk-Nusair (VWN) [23], plus the Becke88-Perdew86 (BP) [24, 25] generalized gradient approximation (GGA). The spin-unrestricted DFT formalism was employed to examine the open-shell Co- and Cu complexes. The structures of the open-shell CoNc(OMe)8 and CuNc(OMe)8 complexes were optimized by assuming a S = 1/2 spin state. The excitation energies were calculated using ordinary (spin-restricted/spin-unrestricted) TDDFT and spinflip (SF)-TDDFT based on a non-collinear representation of the XC potential [26-28]. Vertical absorption energies, Eva, were evaluated at the ground-state geometry. For selected excited states, adiabatic energies, Eadia, were computed according to the expression Eadia = Eve + ΔE, where Eve is the vertical emission energy, which is computed at the TDDFT level using the relaxed excited-state geometry. The ΔE term accounts for the change in energy of the ground state upon deformation to the relaxed geometry of the excited state (for a schematic definition of the calculated energies, see Fig. 10 in Reference 11). Solvent effects on the excitation energies were modeled by the conductor-like continuum solvent model (COSMO) [29-32], using the structures optimized in the gas-phase.
  • 21
    • 85037165203 scopus 로고    scopus 로고
    • ADF; Scientific Computing & Modelling NV: Amsterdam The Netherlands; available from
    • ADF; Scientific Computing & Modelling NV: Amsterdam, The Netherlands; available from http://www.scm.com.
  • 43
    • 85037153599 scopus 로고    scopus 로고
    • One-electron transitions from fully occupied to empty orbitals result in one set of quartet excited states and two sets of doublet states, whereas oneelectron transitions from or into the singly occupied orbital result in doublet states
    • One-electron transitions from fully occupied to empty orbitals result in one set of quartet excited states and two sets of doublet states, whereas oneelectron transitions from or into the singly occupied orbital result in doublet states.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.