Jump to main content
Jump to site search

Issue 32, 2012
Previous Article Next Article

Photochemical dynamics of indolylmaleimide derivatives

Author affiliations


On-the-fly nonadiabatic ab initio molecular dynamics simulations have been carried out for three anionic species of indolylmaleimides (3-(1H-3-indolyl)-2,5-dihydro-1H-2,5-pyrroledione, IM) to clarify the mechanisms of photochemical reactions. The results are obtained for (i) a monovalent anion with a deprotonated indole NH group (IM), (ii) a monovalent anion with a deprotonated maleimide NH group (IM′′) and (iii) a divalent anion with doubly deprotonated indole and the maleimide NH groups (IM2−). Quantum chemical calculations are treated at the three state averaged complete-active space self-consistent field level for 6 electrons in 5 orbitals with the cc-pVDZ basis set (CAS (6, 5) SCF/cc-pVDZ). Molecular dynamics simulations are performed with electronically nonadiabatic transitions included using the Zhu–Nakamura version of the trajectory surface hopping (ZN-TSH) method. It is found that the nonadiabatic transitions occur accompanied by the stretching and shrinking motions of the N(7)–C(8) bond in the case of IM and the C(11)–N(12) bond in IM2− rather than the twisting motion of the dihedral angle. We also found that the ultrafast S2 → S1 nonadiabatic transitions occur through the conical intersection (CoIn) right after photoexcitation to S2 in IM and IM2−. Furthermore, the S1 → S0 nonadiabatic transitions are found to take place in IM. It is concluded that IM2− would mainly contribute to the photoemission, because the S1 ← S0 and S2 ← S0 transitions of IM′′ are dipole-forbidden transitions and, moreover, IM2− is found to be the only species to stay in the S1 state without non-radiative decay.

Graphical abstract: Photochemical dynamics of indolylmaleimide derivatives

Back to tab navigation

Supplementary files

Publication details

The article was received on 20 Apr 2012, accepted on 26 Jun 2012 and first published on 17 Jul 2012

Article type: Paper
DOI: 10.1039/C2CP41269A
Phys. Chem. Chem. Phys., 2012,14, 11546-11555

  •   Request permissions

    Photochemical dynamics of indolylmaleimide derivatives

    T. Murakami, M. Nakazono, A. Kondorskiy, T. Ishida and S. Nanbu, Phys. Chem. Chem. Phys., 2012, 14, 11546
    DOI: 10.1039/C2CP41269A

Search articles by author