Theoretical Study of Solvent Effects on the Ground and Low-Lying Excited Free Energy Surfaces of a Push鈥揚ull Substituted Azobenzene

详细信息    查看全文

• 作者：Jose C. Corchado ; M. Luz S谩nchez ; Ignacio Fdez. Galv谩n ; M. Elena Mart铆n ; Aurora Mu帽oz-Losa ; Rute Barata-Morgado ; Manuel A. Aguilar
• 刊名：Journal of Physical Chemistry B
• 出版年：2014
• 出版时间：October 30, 2014
• 年：2014
• 卷：118
• 期：43
• 页码：12518-12530
• 全文大小：838K
• ISSN：1520-5207

文摘

The ground and low-lying excited free energy surfaces of 4-amino-4鈥?cyano azobenzene, a molecule that has been proposed as building block for chiroptical switches, are studied in gas phase and a variety of solvents (benzene, chloroform, acetone, and water). Solvent effects on the absorption and emission spectra and on the cis鈥搕rans thermal and photo isomerizations are analyzed using two levels of calculation: TD-DFT and CASPT2/CASSCF. The solvent effects are introduced using a polarizable continuum model and a QM/MM method, which permits one to highlight the role played by specific interactions. We found that, in gas phase and in agreement with the results found for other azobenzenes, the thermal cis鈥搕rans isomerization follows a rotation-assisted inversion mechanism where the inversion angle must reach values close to 180掳 but where the rotation angle can take almost any value. On the contrary, in polar solvents the mechanism is controlled by the rotation of the CN鈺怤C angle. The change in the mechanism is mainly related to a better solvation of the nitrogen atoms of the azo group in the rotational transition state. The photoisomerization follows a rotational pathway both in gas phase and in polar and nonpolar solvents. The solvent introduces only small modifications in the n蟺* free energy surface (S₁), but it has a larger effect on the 蟺蟺* surface (S₂) that, in polar solvents, gets closer to S₁. In fact, the S₂ band of the absorption spectrum is red-shifted 0.27 eV for the trans isomer and 0.17 eV for the cis. In the emission spectrum the trend is similar: only S₂ is appreciably affected by the solvent, but in this case a blue shift is found.