Short-pulse laser irradiation of
a colloidal solution of nanoparticles
is an effective method for fragmenting the nanoparticles and producing
a population of smaller nanoparticles and atomic clusters with properties
desired in various fields of applications, including biology, medicine,
and catalysis. To investigate the mechanisms involved in the fragmentation,
we develop a computational model capable of realistic treatment of
a variety of interrelated processes occurring on different time and
length scales, from the electronic excitation by the laser pulse,
to the electron–phonon energy transfer and an explosive phase
decomposition of the superheated nanoparticle, and to the generation
and collapse of a nanobubble in a liquid environment. The application
of the model to simulation of laser fragmentation of a Au nanoparticle
in water has revealed two distinct channels of the formation of the
fragmentation products. The first channel involves the direct injection
of compact nanodroplets propelled by the phase explosion of the irradiated
nanoparticle deep into the water environment. The second channel of
the nanoparticle formation involves a more gradual growth through
agglomeration of numerous atomic clusters embedded into a narrow region
of water surrounding the laser-induced nanobubble. This channel produces
irregularly shaped nanoparticles and leads to a rapid decline of the
population of atomic clusters on the timescale of nanoseconds. All
the clusters and nanoparticles experience an ultrafast quenching by
the water environment and feature a high density of twin boundaries
and other crystal defects, which may enhance the density of active
sites for the catalytic applications of the nanoparticles. The computational
predictions of the prompt generation of a high concentration of the
fragmentation products in a relatively narrow shell-like region on
the outer side of the nanobubble, as well as the rapid solidification
of atomic clusters and nanoparticles at the early stage of the nanobubble
formation, have important practical implications for the design of
new methods aimed at achieving an improved control over the size,
shape, and defect structures of nanoparticles produced by laser fragmentation
in liquids.