Theoretical Analysis of the Electronic Structure and Optical Properties of DNA-Stabilized Silver Cluster Ag16Cl2 in Aqueous Solvent

24 May 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


DNA-stabilized silver nanoclusters with 10 to 30 silver atoms are by construction ideal candidates for biocompatible bright fluorescent emitters but their electronic structure is not well understood. Here, using density functional theory (DFT), we analyze the ground-state electronic structure and optical absorption of a bright NIR-emitting cluster Ag16Cl2 which is stabilized by two DNA strands of 9-base sequence 5’-CACCTAGCG-3’ and whose atomic structure was very recently confirmed to have two chlorides bound to the silver core. We are able to (i) unambiguously assign the charge of this cluster in aqueous solvent, (ii) analyze the details of silver–DNA interactions and their effect on the cluster charge, (iii) analyze the character of low-energy optical absorption peaks and the involved electron orbitals and make a first assessment on circular dichroism, and (iv) evaluate the suitability of various DFT exchange-correlation functionals via benchmarking to experimental optical data. This work lays out a baseline for all future theoretical work to understand the electronic, chiroptical and fluorescence properties of these fascinating bio-compatible nanostructures.


optical absorption
circular dichroism


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.
Comment number 1, Hannu Häkkinen: Aug 09, 2023, 09:23

A slightly expanded version of this manuscript was published as a regular article in JPC C.