Electronically excited states and photochemical reaction mechanisms of β-glucose

Phys Chem Chem Phys. 2014 Jan 7;16(1):38-47. doi: 10.1039/c3cp52359d.

Abstract

Carbohydrates are important molecular components of living matter. While spectroscopic and computational studies have been performed on carbohydrates in the electronic ground state, the lack of a chromophore complicates the elucidation of the excited-state properties and the photochemistry of this class of compounds. Herein, we report on the first computational investigation of the singlet photochemistry of β-glucose. It is shown that low-lying singlet excited states are of nσ* nature. Our computations of the singlet vertical excitation energies predict absorption from 6.0 eV onward. Owing to a dense manifold of weakly-absorbing states, a sizable and broad absorption in the ultraviolet-C range arises. We have explored two types of photochemical reaction mechanisms: hydrogen-detachment processes for each of the five O-H groups and a C-O ring-opening process. Both types of reactions are driven by repulsive nσ* states that are readily accessible from the Franck-Condon region and lead to conical intersections in a barrierless fashion. We have optimized the geometries of the conical intersections involved in these photochemical processes and found that these intersections are located around 5.0 eV for the O-H hydrogen-detachment reactions and around 4.0 eV for the C-O ring-opening reaction. The energies of all conical intersections are well below the computed absorption edge. The calculations were performed using linear-response methods for the computation of the vertical excitation energies and multiconfigurational methods for the optimization of conical intersections and the computation of energy profiles.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Absorption
  • Carbohydrate Conformation
  • Electrons*
  • Glucose / chemistry*
  • Hydrogen / chemistry
  • Models, Molecular
  • Photochemical Processes*
  • Quantum Theory

Substances

  • Hydrogen
  • Glucose