Vibrational and anion photoelectron spectroscopy of transition metal clusters

The understanding of chemical bonding and of the resulting atomic ar rangements is a central topic in molecular physics. The bonding mechanisms of transition metal atoms still constitute a challenge in their theoretical de scription due to the massive number of valence electrons. Moreover, small transition metal clusters and their complexes may serve as models for catalytic systems of interest for science and technology. The goal of this thesis is the characterization of the geometric and electronic structures of isolated transition metal clusters in the gas phase and, consequently, a better understanding of their bonding nature. The first part of the thesis encompasses experimental results and conclusions for the anionic platinum trimer (Pt3-) and the tantalum nitride anion (TaN−). The data is obtained through anion photoelectron spectroscopy via velocity map imaging (VMI), which permits the simultaneous measurement of photoelectron spectra and photoelectron angular distributions (PADs). The study on TaN− reports the first photoelectron spectra of this diatomic molecule. The spectroscopic assignments, carried out with the support of previous theoretical and experimental works, provide measurements of the adiabatic electron affinity (EAad) and of the vibrational frequencies of the anion and the neutral molecule. In addition, the analysis of the PADs reveals the existence of two core excited shape resonances and disentangles the hybridization of a key molecular orbital. In the study of Pt3-, the experiment is performed in the slow electron velocity map imaging (SEVI) mode to resolve the low-frequency vibrational structure, characteristic of metal clusters. A plethora of information is obtained with the support of density functional theory (DFT) calculations, which includes the presence of two isomeric forms (triangular and linear) and hints at pseudo Jahn-Teller and Jahn-Teller effects. Some of the PADs reveal an oscillatory energetic dependence that, according to the quantum analogy established by Fano with the Young’s double slit experiment, is interpreted as interferometric effects in the linear isomer. In the second part of the thesis, the characterizations of CoArn+(n=3 to 6), Con−mMnmArx+ (n=3 to 14; m=0 to 2) and saturated cationic Ru cluster carbonyls Run(CO)m+ (n=1 to 8) via (far-)infrared multiple photon dissociation (IRMPD) spectroscopy, more suitable to obtain structural information on the studied complexes, are reported. The investigation on CoArn+ readdresses the question on the nature of the interaction between the metal cation and the rare gas atom by proposing some amount of covalency in the bonding. Motivated by the role of ruthenium as catalyst for CO methanation in the Fischer-Tropsch process, the composition and structures of saturated cationic ruthenium carbonyls are studied. Their IR spectra are obtained in the range of the C-O stretches, Ru-CO stretches and deformation modes. Structural assignment is achieved with the aim of DFT calculations and the results corroborate former predictions. Finally, IR spectra of Con−mMnmArx+ are presented and discussed in comparison to those of pure cobalt clusters with the purpose of motivating future theoretical studies that may solve the puzzling structures of these binary metal clusters.

Author dc:creator

• Yubero Valdivielso, David

Advisors dc:contributor.advisor

• Meijer, Gerard
• von Helden, Gert
• Fielicke, André

Licence dc:rights.uri

• https://creativecommons.org/licenses/by/4.0/

Language dc:language.iso

en

Identifier URI

http://dx.doi.org/10.14279/depositonce-16087

OAI identifier oai:identifier

oai:depositonce.tu-berlin.de:11303/17306