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Theoretical Chemistry Accounts

, Volume 116, Issue 1–3, pp 148–159 | Cite as

A first principles approach to optimal control

  • Leticia González
  • Jürgen Full
Regular Article

Abstract

This article shows that by using ab initio or first principle calculations it is possible to obtain reliable ingredients needed to simulate pump-probe and optimal control experiments. Our experimental challenge is to elucidate the reaction mechanism behind an optimal pulse tailored to maximize ionization in the system CpMn(CO)3, while avoiding CO dissociation. Starting from MRCI/CASSCF potential energy curves calculated along the relevant CO fragmentation channel, we use the resulting MRCI wave function to estimate non-adiabatic couplings, as well as neutral-to-neutral and neutral-to-ionic dipole couplings. The state-of-the-art potentials and couplings serve to perform wave packet propagations which simulate the femtosecond pump-probe spectra that explain the features shown in the experimental optimal pulse.

Keywords

Organometallics Multiconfigurational methods Reaction dynamics Femtochemistry Optimal control 

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Copyright information

© Springer-Verlag 2005

Authors and Affiliations

  1. 1.Institut für Chemie and BiochemieFreie Universität BerlinBerlinGermany

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