Photochemical Au(I)–Au(I) Bond Formation: A Battle between Intersystem Crossing and Internal Conversion

Tang, Diandong; Liao, Can; Taub, Maxwell; Schatz, George C.; Guo, Hua; Li, Xiaosong

doi:10.1021/acs.jpclett.5c00310

Photochemical Au(I)–Au(I) Bond Formation: A Battle between Intersystem Crossing and Internal Conversion

Journal Article · Tue Apr 08 00:00:00 EDT 2025 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5c00310· OSTI ID:3011597

^[1]; Liao, Can ^[1]; ^[1]; ^[2]; ^[3]; ^[1]

University of Washington, Seattle, WA (United States)
Northwestern University, Evanston, IL (United States)
University of New Mexico, Albuquerque, NM (United States)

The transition metal complex Au(CN)₂^– has provided experimental evidence of photoinduced bond formation between Au(I) atoms in solution. However, the underlying photochemical driving force for this bond formation reaction remains unclear. In this study, we investigate the ultrafast Au–Au bonding process in the [Au(CN)₂]₂^2– dimer using nonadiabatic dynamics simulations that incorporate intersystem crossing and internal conversion pathways. Reaction pathways and transitions among photochemically accessible singlet and triplet excited states are analyzed. Computational results indicate that intersystem crossing is the primary driving force in the early stages of ultrafast photochemical dynamics, while internal conversion among triplet states plays a critical role after the system stabilizes in a higher-lying triplet state. Furthermore, this work provides a mechanistic perspective on modulating photochemical reactions by tuning the relative strengths of spin–orbit coupling and nonadiabatic coupling.

View Accepted Manuscript (DOE)

Research Organization:: University of New Mexico, Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); Air Force Office of Scientific Research (AFOSR)

Grant/Contract Number:: SC0015997; AC02-06CH11357

OSTI ID:: 3011597

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 15 Vol. 16; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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