Ground and excited states of zinc phthalocyanine, zinc tetrabenzoporphyrin, and azaporphyrin analogs using DFT and TDDFT with Franck-Condon analysis

Journal Article · Sat Mar 07 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4913757· OSTI ID:22416222

Huang, Liang; Fleetham, Tyler; Adams, James B.; Li, Jian ^[1]

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1. Material Science and Engineering Program, Arizona State University, Tempe, Arizona 85287 (United States)

The electronic structure of eight zinc-centered porphyrin macrocyclic molecules are investigated using density functional theory for ground-state properties, time-dependent density functional theory (TDDFT) for excited states, and Franck-Condon (FC) analysis for further characterization of the UV-vis spectrum. Symmetry breaking was utilized to find the lowest energy of the excited states for many states in the spectra. To confirm the theoretical modeling, the spectroscopic result from zinc phthalocyanine (ZnPc) is used to compare to the TDDFT and FC result. After confirmation of the modeling, five more planar molecules are investigated: zinc tetrabenzoporphyrin (ZnTBP), zinc tetrabenzomonoazaporphyrin (ZnTBMAP), zinc tetrabenzocisdiazaporphyrin (ZnTBcisDAP), zinc tetrabenzotransdiazaporphyrin (ZnTBtransDAP), and zinc tetrabenzotriazaporphyrin (ZnTBTrAP). The two latter molecules are then compared to their phenylated sister molecules: zinc monophenyltetrabenzotriazaporphyrin (ZnMPTBTrAP) and zinc diphenyltetrabenzotransdiazaporphyrin (ZnDPTBtransDAP). The spectroscopic results from the synthesis of ZnMPTBTrAP and ZnDPTBtransDAP are then compared to their theoretical models and non-phenylated pairs. While the Franck-Condon results were not as illuminating for every B-band, the Q-band results were successful in all eight molecules, with a considerable amount of spectral analysis in the range of interest between 300 and 750 nm. The π-π{sup ∗} transitions are evident in the results for all of the Q bands, while satellite vibrations are also visible in the spectra. In particular, this investigation finds that, while ZnPc has a D{sub 4h} symmetry at ground state, a C{sub 4v} symmetry is predicted in the excited-state Q band region. The theoretical results for ZnPc found an excitation energy at the Q-band 0-0 transition of 1.88 eV in vacuum, which is in remarkable agreement with published gas-phase spectroscopy, as well as our own results of ZnPc in solution with Tetrahydrofuran that are provided in this paper.

• OSTI ID: 22416222
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTRA
COMPARATIVE EVALUATIONS
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
EXCITATION
EXCITED STATES
FRANCK-CONDON PRINCIPLE
GROUND STATES
MOLECULES
PHTHALOCYANINES
PORPHYRINS
SYMMETRY BREAKING
SYNTHESIS
TETRAHYDROFURAN
TIME DEPENDENCE
ZINC COMPOUNDS