Theoretical study of cyclohexadiene/hexatriene photochemical interconversion using spin-Flip time-Dependent density functional theory

Abstract

The photochemical interconversion between 1,3-cyclohexadiene (CHD) and all-cis-hexatriene (cZc-HT) is reinvestigated using spin-flip time-dependent density functional theory in combination with various hybrid functionals, BHHLYP functional showing the best performance. The critical geometries of the ground, S${}_0$, and the first two excited-state, S${}_1$ and S${}_2$, potential energy surfaces, such as, various minima, transition state, minimum-energy crossing points between S${}_2$/S${}_1$ and S${}_1$/S${}_0$ show an excellent agreement with those obtained by multireference wave function methods. Our results show how a low-cost method based on DFT can successfully describe and characterise the most important geometries on the potential energy surfaces along the ring-opening/closure reaction coordinate involved in the CHD to cZc-HT photoconversion.

GRAPHICAL ABSTRACT

Keywords:

• Photochemistry
• electrocyclic reactions
• spin-Flip
• conical intersection
• minimum-energy crossing point

Acknowledgments

This work is part of Innovational Research Incentives Scheme Vidi 2017 with project number 016.Vidi.189.044, which is financed by the Dutch Research Council (NWO).

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

This work is part of Innovational Research Incentives Scheme Vidi 2017 with project number 016.Vidi.189.044, which is financed by the Dutch Research Council.