Jump to main content
Jump to site search

Volume 163, 2013
Previous Article Next Article

Quantum-classical effective-modes dynamics of the ππ* → nπ* decay in 9H-adenine. A quadratic vibronic coupling model

Author affiliations

Abstract

We present mixed quantum-classical simulation of the internal conversion between the lowest energy ππ* (SLa) and nπ* (Sn) excited electronic states in adenine in the gas phase, adopting a quadratic vibronic model (QVC), parametrized with the help of PBE0 density functional calculations. Our approach is based on a hierarchical representation of the QVC Hamiltonian and a subsequent treatment of the most relevant coordinates at accurate time-dependent quantum level and of the other ‘bath’ modes at classical level. We predict an ultrafast transfer (∼30 fs) of ≈75% of the initial population excited on SLa to Sn. Within an adiabatic picture, on the same timescale the wave packet concentrates almost completely on the lowest S1 state, where however it shows a very broad distribution with different characteristics (due to the different ‘diabatic’ character). It is shown that the proposed methodology offers a practicable route to describe the quantum dynamics of internal conversion processes in large semi-rigid systems.

Back to tab navigation

Supplementary files

Publication details

The article was received on 11 Dec 2012, accepted on 10 Jan 2013 and first published on 11 Jan 2013


Article type: Paper
DOI: 10.1039/C3FD20147C
Citation: Faraday Discuss., 2013,163, 223-242
  •   Request permissions

    Quantum-classical effective-modes dynamics of the ππ* → nπ* decay in 9H-adenine. A quadratic vibronic coupling model

    D. Picconi, F. J. Avila Ferrer, R. Improta, A. Lami and F. Santoro, Faraday Discuss., 2013, 163, 223
    DOI: 10.1039/C3FD20147C

Search articles by author

Spotlight

Advertisements