Publisher: American Chemical Society (ACS)

Issue: 21

License: [{"start"=>{"date-parts"=>[[2016, 11, 11]], "date-time"=>"2016-11-11T00:00:00Z", "timestamp"=>1478822400000}, "content-version"=>"vor", "delay-in-days"=>16, "URL"=>"http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html"}]

Publication date(s): 2016/11/03 (print) 2016/10/26 (online)

Pages: 4414-4419

Volume: 7 Issue: 21

Journal: The Journal of Physical Chemistry Letters

Link: [{"URL"=>"http://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.6b02181", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acs.jpclett.6b02181", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

URL: http://dx.doi.org/10.1021/acs.jpclett.6b02181

We present a study of the transitional pathways between high-symmetry structural motifs for AgAu nanoparticles, with a specific focus on controlling the energetic barriers through chemical design. We show that the barriers can be altered by careful control of the elemental composition and chemical arrangement, with core@shell and vertex-decorated arrangements being specifically influential on the barrier heights. We also highlight the complexity of the potential and free energy landscapes for systems where there are low-symmetry geometric motifs that are energetically competitive to the high-symmetry arrangements. In particular, we highlight that some core@shell arrangements preferentially transition through multistep restructuring of low-symmetry truncated octahedra and rosette-icosahedra, instead of via the more straightforward square-diamond transformations, due to lower energy barriers and competitive energetic minima. Our results have promising implications for the continuing efforts in bespoke nanoparticle design for catalytic and plasmonic applications.