ONIOM approach for non-adiabatic on-the-fly molecular dynamics demonstrated for the backbone controlled Dewar valence isomerization.
Non-adiabatic on-the-fly molecular dynamics (NA-O-MD) simulations require the electronic wavefunction, energy gradients, and derivative coupling vectors in every timestep. Thus, they are commonly restricted to the excited state dynamics of molecules with up to ≈20 atoms. We discuss an approximation that combines the ONIOM(QM:QM) method with NA-O-MD simulations to allow calculations for larger molecules. As a proof of principle we present the excited state dynamics of a (6-4)-lesion containing dinucleotide (63 atoms), and especially the importance to include the confinement effects of the DNA backbone. The method is able to include electron correlation on a high level of theory and offers an attractive alternative to QM:MM approaches for moderate sized systems with unknown force fields.
Department of Chemistry, Ludwig-Maximilians University Munich, Butenandtstrasse 5-13, 81377 Munich, Germany. bfingerh@uci.edu
Benjamin P
BP
Fingerhut
Sven
S
Oesterling
Karin
K
Haiser
Korbinian
K
Heil
Andreas
A
Glas
Wolfgang J
WJ
Schreier
Wolfgang
W
Zinth
Thomas
T
Carell
Regina
R
de Vivie-Riedle
D000465:Algorithms; D004247:DNA / Q000737:chemistry; D004583:Electrons; D007536:Isomerism; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D013942:Thymine Nucleotides / Q000737:chemistry*
D013942:Thymine Nucleotides; D004247:DNA