Measurement and theoretical characterization of electronic absorption spectrum of neutral chrysene (C18H12) and its positive ion in H3BO3 matrix

The ultraviolet and visible spectrum of chrysene and its radical cation formed by ultraviolet irradiation were measured in boric acid glass at room temperature. The theoretical electronic absorption spectrum of any polycyclic aromatic hydrocarbon (PAH) in boric acid matrix is calculated for the first time using semi empirical methods. Earlier reported theoretical results of electronic spectrum are calculated in free state and the results are compared with the spectrum of aromatic systems in glassy or other matrices. The interaction between the trapped PAHs (neutral and ions) and its environment induces strong perturbations of the energy levels which results in large shifts of the electronic transitions as compared to the ideal case of a free, isolated PAH molecule. This shifting due to perturbation has largely been ignored in earlier calculations, while comparing the calculations with the experimentally measured spectrum, in other matrices. The spectrum of singlet and doublet state of chrysene are computed in aqueous medium and also in free state to estimate the spectral shift. Several other geometric (bond length and bond angles) and spectroscopic parameters of chrysene like difference of HOMO-LUMO, ionization potential, dipole moment and polarizability are calculated using semi empirical methods, namely Austin Model 1 (AM1) and Parametric Method 3 (PM3). To get an idea about how the symmetry of chrysene molecule varies upon ionization, the mean polarizability (α) as well as its tensor components αxx, αyy and αzz are calculated within a field of 0.005 a.u. The lasing action in neutral chrysene and in its cationic form is also discussed for the first time.