Time-dependent density functional theory applied to clusters and molecules in contact with an environment

• Main Author: Dinh, Phuong Mai
• Language: English
• Published: Université Paul Sabatier - Toulouse III 2009
• Subjects: [PHYS:PHYS:PHYS_ATM-PH] Physics/Physics/Atomic and Molecular Clusters; [PHYS:PHYS:PHYS_ATM-PH] Physique/Physique/Agrégats Moléculaires et Atomiques; TDDFT; molecular dynamics; clusters; environment; electronic excitation; electronic emission
• Online Access: http://tel.archives-ouvertes.fr/tel-00981941; http://tel.archives-ouvertes.fr/docs/00/98/19/41/PDF/hdr.pdf

We present recent theoretical and methodological explorations on the dynamics of sodium clusters in the framework of Time-Dependent Density Functional Theory (TDDFT), coupled non-adiabatically to Molecular-Dynamics (MD). In particular, a hierarchical approach, in the spirit of Quantum-Mechanical/Molecular-Mechanical methods, has been developed for the description of metal clusters in interaction with a dynamically polarizable substrate, as rare gases or MgO. Numerous examples of application of this approach (Na clusters in or on Ar substrate, Na clusters deposited on MgO; optical response, dynamical deposition, laser irradiation, ...) are reviewed. We also briefly discuss complementing research activities. Formal developments on the Self-Interaction Correction issue in DFT and TDDFT are discussed in a word. We have furthermore extended our TDDFT-MD theory to the case of organic (C, N, O, H made) systems and a few examples of investigated dynamical processes are presented. Recent calculations of photoelectron angular distributions of free metal clusters are reported as well. We finally sketch with some perspectives for the years to come.