Computational study of the adamantane cation: simulations of spectroscopy, fragmentation dynamics, and internal conversion

• Published in: Theoretical chemistry accounts Vol. 142; no. 8
• Main Authors: Roy, Bonasree, Titov, Evgenii, Saalfrank, Peter
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.08.2023; Springer Nature B.V
• Subjects: Astrochemistry; Atomic/Molecular Structure and Spectra; Cations; Chemistry; Chemistry and Materials Science; Diamonds; Excitation; Fragmentation; Inorganic Chemistry; Internal conversion; Molecular dynamics; Nanomaterials; Optoelectronics; Organic Chemistry; Photoelectrons; Physical Chemistry; Simulation; Spectrum analysis; Theoretical and Computational Chemistry; Spectra; Cation; Internal conversion; Adamantane; Surface hopping; Fragmentation
• ISSN: 1432-881X; 1432-2234
• DOI: 10.1007/s00214-023-03006-8

Diamondoids, of which adamantane (C 10 H 16 ) is the simplest representative, constitute an intriguing class of carbon based nanomaterials with interesting chemical, mechanical and opto-electronic properties. While neutral diamondoids have been extensively studied for decades, their cationic counterparts were a subject of recent experimental investigations motivated by their potential role in astrochemistry. Here, we perform a computational study of the adamantane cation (C 10 H 16 + ) complementing the recent experimental findings. Specifically, we extend earlier theoretical work on vibrationally resolved electronic spectroscopy by accounting for the higher lying electronically excited states of the cation in the absorption and photoelectron spectra. We also perform adiabatic and nonadiabatic (surface hopping) molecular dynamics simulations to study (fast) fragmentation processes and electronic relaxation of C 10 H 16 + . Our simulations reveal that after excitation with near-infrared–ultraviolet photons, the adamantane cation undergoes an ultrafast internal conversion to the ground (doublet) state (on a time scale of 10–100 fs depending on initial excitation energy) which can be followed by a fast fragmentation, predominantly H loss. The yield of the ultrafast hydrogen dissociation as a function of excitation energy is reported.