title: Quantum-chemical calculations of the electronic structure of 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene derivatives.
abstract: The UV-Visible absorption spectra of six, newly synthesized donor-substituted 2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene have been measured in methylcyclohexane (MCH) and assigned with the help of quantum-chemical calculations. Our calculations have been performed to assess information regarding the electronic state energy values, corresponding oscillator strengths, x-, y-, z-components of the transition dipole moments and molecular orbitals involved in the main electronic transitions of the studied compounds. Additionally, the experimental absorption transition dipole moments were calculated, on the basis of spectroscopic data, and compared with results of our quantum-chemical calculations. On the basis of the experimental results and quantum-chemical calculations, it was shown that the long-wavelength absorption band involves an overlap of three electronic transitions of different character. For all studied donor-acceptor (D-A) compounds in vapour-phase, the long-wavelength transition (S0→S1) does not possess charge transfer character, whereas the S0→S2 transition possesses electron transfer character e.g., π-electrons of the acceptor moiety are moved to the donor part. Moreover, it is found that the electronic structure of the studied biphenyl derivatives can be approximately described within composite-model of decoupled moieties: donor and acceptor.
authors.affiliation: Institute of Experimental Physics, University of Gdańsk, Wita Stwosza 57, 80-952 Gdańsk, Poland. fizmj@univ.gda.pl
authors.forename: M
authors.initials: M
authors.lastname: Józefowicz
authors.forename: A
authors.initials: A
authors.lastname: Bajorek
authors.forename: M
authors.initials: M
authors.lastname: Pietrzak
authors.forename: J R
authors.initials: JR
authors.lastname: Heldt
mesh_terms: D000042:Absorption; D004396:Coloring Agents / Q000737:chemistry; D004583:Electrons; D008958:Models, Molecular; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D009570:Nitriles / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: C585880:2-amino-1,3-dicyano-5,6,7,8-tetrahydronaphthalene; D004396:Coloring Agents; D009281:Naphthalenes; D009570:Nitriles; C031721:naphthalene
keywords: Donor–acceptor system; Intramolecular charge transfer; Quantum-chemical calculations; Transition dipole moment