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Theoretical studies of copper clusters

Courtney Marie Sams

Published Jan 1, 2013• 0 citations
OpenAlex

Abstract

We introduce an experimental platform designed around a thermo-mechanical helium fountain, which is aimed at investigating spectroscopy and dynamics of atoms and molecules in the superfluid, and at its vapor interface.Laser ablation of copper, efficient cooling and transport of Cu and Cu 2 through helium vapor (1.5 K < T < 20 K), formation of linear and T-shaped Cu 2 -He complexes, and their continuous evolution into large Cu 2 -He n clusters and droplets, are among the processes that are illustrated.Reflection is the dominant quantum scattering channel of translationally cold copper atoms (T = 1.7 K) at the fountain interface.Cu 2 dimers mainly travel through the fountain unimpeded.However, the conditions of fountain flow and transport of molecules can be controlled to demonstrate injection, and in particular injection into a non-divergent columnar fountain with a plug velocity of ca. 1 m/s.The experimental observables are interpreted with the aid of bosonic density functional theory calculations and ab initio interaction potentials.

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We introduce an experimental platform designed around a thermo-mechanical helium fountain, which is aimed at investigating spectroscopy and dynamics of atoms and molecules in the superfluid, and at its vapor interface.Laser ablation of copper, efficient cooling and transport of Cu and Cu 2 through helium vapor (1.5 K < T < 20 K), formation of linear and T-shaped Cu 2 -He complexes, and their continuous evolution into large Cu 2 -He n clusters and droplets, are among the processes that are illustrated.Reflection is the dominant quantum scattering channel of translationally cold copper atoms (T = 1.7 K) at the fountain interface.Cu 2 dimers mainly travel through the fountain unimpeded.However, the conditions of fountain flow and transport of molecules can be controlled to demonstrate injection, and in particular injection into a non-divergent columnar fountain with a plug velocity of ca. 1 m/s.The experimental observables are interpreted with the aid of bosonic density functional theory calculations and ab initio interaction potentials.
We introduce an experimental platform designed around a thermomechanical helium fountain, which is aimed at investigating spectroscopy and dynamics of atoms and molecules in the superfluid and at its vapor interface. Laser ablation of copper, efficient cooling and transport of Cu and Cu(2) through helium vapor (1.5 K < T < 20 K), formation of linear and T-shaped Cu(2)-He complexes, and their continuous evolution into large Cu(2)-He(n) clusters and droplets are among the processes that are illustrated. Reflection is the dominant quantum scattering channel of translationally cold copper atoms (T = 1.7 K) at the fountain interface. Cu(2) dimers mainly travel through the fountain unimpeded. However, the conditions of fountain flow and transport of molecules can be controlled to demonstrate injection and, in particular, injection into a nondivergent columnar fountain with a plug velocity of about 1 m/s. The experimental observables are interpreted with the aid of bosonic density functional theory calculations and ab initio interaction potentials.
Many microscopic properties of the only natural superfluid element helium have become available within the last 18 years through a number of novel experiments. The diffraction of matter-waves of small helium clusters has established the unusually large bond distance (5.2 nm) and extremely weak binding energy (10−7 eV) of the dimer and other exotic properties of small helium clusters. The high-resolution spectroscopy of closed-shell chromophore molecules attached to small clusters or embedded inside large superfluid droplets have revealed that as a result of superfluidity, molecules rotate virtually without friction and that only a handful of He atoms are required for microscopic superfluidity. The frictionless translational motion of atoms and molecules inside the droplets has also been observed. These and a number of other experiments demonstrate that helium droplets are the most gentle and coldest of all cryomatrices with enormous potential for a wide range of future applications.
Superfluid helium droplets represent a unique state of matter, which are large clusters of helium typically containing approximately 103-1011 helium atoms and exhibit remarkable properties such as superfluidity, a very low temperature (0.37 K) and high thermal conductivity. This PhD project investigates two novel aspects of superfluid helium droplets: the use of superfluid helium nanodroplets as the nanoreactors to grow magnetic nanoparticles and the generation and exploration of quantum vortices in a controlled manner. In the first part, we exploit the very low temperature and rapid cooling to develop a new approach for fabricating magnetic nanoparticles. For the very low temperature and the ultrahigh thermal conductivity, superfluid helium can suppress thermal effects during the atom-by-atom growth of magnetic nanoparticles, making the relatively weak exchange interactions (compared with metallic bonding) the driving force. As a result, the atomic spins align for ferromagnetic elements and thus the magnetic moments of nanoparticles are maximized. In particular, we focus on iron nanoparticles coated by a gold shell and investigate their properties by electron microscopy (for structural investigation) and x-ray circular dichroism (XMCD), for magnetic property measurement) at the Diamond Light Source. We first study mass spectrometry of small iron clusters and observed abnormal behaviours. Unlike other molecular clusters formed in helium droplets such as water, gold and silver, which typically follow a Poisson distribution, Fe+ channel was found to be far greater than that of FeN+ (N = 2-8) clusters. We postulate this as an indicator for the formation of high-spin iron clusters inside superfluid helium and attempt to provide an interpretation based on DFT calculations. However, XMCD showed an expected low magnetisation for Fe/Au core-shell nanoparticles which is even lower than iron oxide nanoparticles, indicating that the neutral Fe atoms are oxidized into Fe2+ within the nanoparticles which is magnetically inert. This is accounted by the very high electron negativity of Au atoms and the alloying effect during the growth of nanoparticles, which dismisses the magnetic properties. Our work shows that the choice of protective shell is important to maintain the magnetic properties of iron nanoparticles and points the direction for the next-step research. The second part presents a breakthrough in quantum vortex research. We demonstrate a novel method for generating controlled vortex arrays in superfluid helium droplets through collisions with cesium ions. Subsequential addition of metal atoms (Ag and Au) to helium droplets and the formation of nanodroplets allow the vortex lattices to be imaged after the nanoparticles are deposited onto a solid surface. By this approach we have revealed a record-high vortex density of 5.6×10¹⁴ m⁻², exceeding previous observations in bulk superfluid helium by more than six orders of magnitude. This unprecedented vortex density opens new possibilities for studying quantum hydrodynamics at extreme angular momenta and investigating quantum turbulence in previously inaccessible regimes. Through detailed theoretical analysis and experimental characterization, this work establishes superfluid helium droplets as a versatile platform for both materials synthesis and fundamental research. Our findings not only advance the understanding of superfluidity but also provide a new pathway for developing high-performance magnetic nanomaterials that can potentially revolutionize biomedical science and technologies.
In this thesis, quantum dynamical simulations are performed in order to describe the vibrational motion of diatomic molecules in a highly quantum environment, so-called helium droplets. We aim to reproduce and explain experimental findings which were obtained from dimers on helium droplets. Nanometer-sized helium droplets contain several thousands of 4-He atoms. They serve as a host for embedded atoms or molecules and provide an ultracold “refrigerator” for them. Spectroscopy of molecules in or on these droplets reveals information on both the molecule and the helium environment. The droplets are known to be in the superfluid He II phase. Superfluidity in nanoscale systems is a steadily growing field of research. Spectra obtained from full quantum simulations for the unperturbed dimer show deviations from measurements with dimers on helium droplets. These deviations result from the influence of the helium environment on the dimer dynamics. In this work, a well-established quantum optical master equation is used in order to describe the dimer dynamics effectively. The master equation allows to describe damping fully quantum mechanically. By employing that equation in the quantum dynamical simulation, one can study the role of dissipation and decoherence in dimers on helium droplets. The effective description allows to explain experiments with Rb-2 dimers on helium droplets. Here, we identify vibrational damping and associated decoherence as the main explanation for the experimental results. The relation between decoherence and dissipation in Morse-like systems at zero temperature is studied in more detail. The dissipative model is also used to investigate experiments with K-2 dimers on helium droplets. However, by comparing numerical simulations with experimental data, one finds that further mechanisms are active. Here, a good agreement is obtained through accounting for rapid desorption of dimers. We find that decoherence occurs in the electronic manifold of the molecule. Finally, we are able to examine whether superfluidity of the host does play a role in these experiments.
Below Tλ = 2.17 K, bulk 4He is a superfluid and has a non-zero Bose-Einstein condensate fraction. This work will focus primarily on how phenomena such as superfluidity, Bose condensation and superfluid vortices are manifested in microscopic, inhomogeneous helium systems. Path Integral Monte Carlo is a powerful method for calculating the equilibrium properties of quantum systems at finite temperature. We have achieved linear scaling of computer time with number of particles through the use of neighbor lists, allowing us to simulate systems of several thousand atoms. We have derived a local superfluid estimator and used it to examine the microscopic superfluid response around a molecule rotating in a helium nanodroplet. We found that the first solvation layer is well-described by a two dimensional superfluid, with thermal excitations occuring at a lower temperature than in bulk helium. The effective moment of inertia of a linear impurity in a helium droplet is calculated, and compared with experimental scattering results. In addition, we calculated the vortex formation energy for both pure droplets and droplets doped with linear impurities, and found that the linear impurities had a negligible impact on the formation energy. A possible spectroscopic signature of vortices in doped helium droplets was suggested. After deriving a local estimator, we calculated the condensate fraction throughout the free helium surface of a semi-infinite slab. These results, along with densitydensity correlation functions, were used to characterize the surface excitations and calculate the extent to which ripplons are present. In addition, the ripplon dispersion relation was calculated using imaginary-time correlation functions, and found to be lll in good agreement with experimental results. Finally, we have calculated the Dey be-Waller factor in solid helium for a range of temperatures and densities, and compared the scaling behavior with the predictions of harmonic theory. The first non-Gaussian contribution to the density distribution was calculated.
This thesis presents experimental and theoretical work performed at the Laser Centre of the Vrije Universiteit in Amsterdam to study laser-cooled metastable triplet helium atoms. Samples containing about 3x10^8 helium atoms-either fermionic helium-3 atoms, bosonic helium-4 atoms or mixtures thereof-are cooled to a temperature around 1 mK and form the starting point of the presented studies. The studies include an investigation of cold ionizing collisions in the absence of resonant light, an investigation of magneto-optical trapping with ultraviolet light, a feasibility study of an atomic fountain clock based on metastable helium-3 atoms and the first demonstration of magneto-optical trapping of an isotopic mixture of metastable helium atoms.