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research article

Classical Force Fields Tailored for QM Applications: Is It Really a Feasible Strategy?

Andreussi, Oliviero  
•
Prandi, Ingrid G.
•
Campetella, Marco
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2017
Journal of Chemical Theory and Computation

Classical molecular dynamics is more and more often coupled to quantum mechanical based techniques as a statistical tool to sample configurations of molecular systems embedded in complex environments. Nonetheless, the classical potentials describing the molecular systems are seldom parametrized to reproduce electronic processes, such as electronic excitations, which are instead very sensitive to the underlining description of the molecular structure. Here, we analyze the challenging case of the peridinin molecule, a natural apocarotenoid responsible for the light-harvesting process in the PCP antenna protein of dinoflagellates. Ground-state structural and vibrational properties, as well as electronic transitions of the pigment are studied by means of quantum-mechanical static and dynamic calculations. Thereafter, classical molecular dynamics simulations are performed with a number of different force-fields, ranging from a popular, general purpose one to refined potentials of increasing level of complexity. From the comparison of classical results with their quantum mechanical counterparts, it appears that, while very poor results are obtained from standard transferrable force-fields, specifically tuned potentials are able to correctly characterize most of the structural and vibrational features of the pigment. Nonetheless, only an advanced parametrization technique is able to give a semiquantitative description of the coupling between vibrations and electronic excitations, thus suggesting that the use of classical MD in combination of QM calculations for the study of photoinduced processes, albeit possible, should be considered with care.

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Type
research article
DOI
10.1021/acs.jctc.7b00777
Web of Science ID

WOS:000412965700004

Author(s)
Andreussi, Oliviero  
Prandi, Ingrid G.
Campetella, Marco
Prampolini, Giacomo
Mennucci, Benedetta
Date Issued

2017

Publisher

Amer Chemical Soc

Published in
Journal of Chemical Theory and Computation
Volume

13

Issue

10

Start page

4636

End page

4648

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
IMX  
Available on Infoscience
November 8, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/142013
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