The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT). CASSCF calculations and absorption and emission spectra simulations by one-photon excitation equations were used to optimize the excited and ground state structures of protonated pyrene isomers. The absorption band was attributed to the S0 -> S1 electronic transition in 1H-Py+, and a band origin was used at 20580.96 cm(-1). The displaced harmonic oscillator approximation and Franck-Condon approximation were used to simulate the absorption spectrum of the (1) (1)A' <- (X) over tilde (1)A' transition of 1H-Py+, and the main vibronic transitions were assigned for the first pi pi(star) state. It shows that the vibronic structures were dominated by one of the eight active totally symmetric modes, with v(15) being the most crucial. This indicates that the electronic transition of the S-1((1)A')state calculated in the adiabatic representation effectively includes a contribution from the adiabatic vibronic coupling through Franck-Condon factors perturbed by harmonic oscillators. The present method can adequately reproduce experimental absorption and fluorescence spectra of a gas phase.
- 2ND-ORDER PERTURBATION-THEORY; EXCITED-STATES; AB-INITIO; ELECTRONIC-TRANSITIONS; AROMATIC-HYDROCARBONS; NEON; SPECTROSCOPY; SIMULATION; CORONENE; CARRIERS