### Abstract

The efficacy of optimal control of quantum dynamics depends on the topology and associated local structure of the underlying control landscape defined as the objective as a function of the control field. A commonly studied control objective involves maximization of the transition probability for steering the quantum system from one state to another state. This paper invokes landscape Hessian analysis performed at an optimal solution to gain insight into the controlled dynamics, where the Hessian is the second-order functional derivative of the control objective with respect to the control field. Specifically, we consider a quantum system composed of coupled primary and secondary subspaces of energy levels with the initial and target states lying in the primary subspace. The primary and secondary subspaces may arise in various scenarios, for example, respectively, as sub-manifolds of ground and excited electronic states of a poly-atomic molecule, with each possessing a set of rotational-vibrational levels. The control field may engage the system through electric dipole transitions that occur either (I) only in the primary subspace, (II) between the two subspaces, or (III) only in the secondary subspace. Important insights about the resultant dynamics in each case are revealed in the structural patterns of the corresponding Hessian. The Fourier spectrum of the Hessian is shown to often be complementary to mechanistic insights provided by the optimal control field and population dynamics.

Original language | English (US) |
---|---|

Pages (from-to) | 18621-18628 |

Number of pages | 8 |

Journal | Physical Chemistry Chemical Physics |

Volume | 17 |

Issue number | 28 |

DOIs | |

State | Published - Jul 28 2015 |

### All Science Journal Classification (ASJC) codes

- Physics and Astronomy(all)
- Physical and Theoretical Chemistry

## Fingerprint Dive into the research topics of 'Hessian facilitated analysis of optimally controlled quantum dynamics of systems with coupled primary and secondary states'. Together they form a unique fingerprint.

## Cite this

*Physical Chemistry Chemical Physics*,

*17*(28), 18621-18628. https://doi.org/10.1039/c5cp02660a