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

Tang, Diandong [University of Washington, Seattle, WA (United States)] (ORCID:0000000322764901); Liao, Can [University of Washington, Seattle, WA (United States)]; Taub, Maxwell [University of Washington, Seattle, WA (United States)] (ORCID:0009000926760271); Schatz, George C. [Northwestern University, Evanston, IL (United States)] (ORCID:0000000158374740); Guo, Hua [University of New Mexico, Albuquerque, NM (United States)] (ORCID:000000019901053X); Li, Xiaosong [University of Washington, Seattle, WA (United States)] (ORCID:0000000173416240)

doi:10.1021/acs.jpclett.5c00310

DOE OSTI · 3011597

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

Tang, Diandong [University of Washington, Seattle, WA (United States)] (ORCID:0000000322764901)·Liao, Can [University of Washington, Seattle, WA (United States)]·Taub, Maxwell [University of Washington, Seattle, WA (United States)] (ORCID:0009000926760271)·Schatz, George C. [Northwestern University, Evanston, IL (United States)] (ORCID:0000000158374740)·Guo, Hua [University of New Mexico, Albuquerque, NM (United States)] (ORCID:000000019901053X)·Li, Xiaosong [University of Washington, Seattle, WA (United States)] (ORCID:0000000173416240)

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Abstract

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.

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Computational chemistry Energy levels Excited states Nonadiabatic coupling Potential energy

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Tang, Diandong [University of Washington, Seattle, WA (United States)] (ORCID:0000000322764901), Liao, Can [University of Washington, Seattle, WA (United States)], Taub, Maxwell [University of Washington, Seattle, WA (United States)] (ORCID:0009000926760271), Schatz, George C. [Northwestern University, Evanston, IL (United States)] (ORCID:0000000158374740), Guo, Hua [University of New Mexico, Albuquerque, NM (United States)] (ORCID:000000019901053X), Li, Xiaosong [University of Washington, Seattle, WA (United States)] (ORCID:0000000173416240). 2025-04-08. Photochemical Au(I)–Au(I) Bond Formation: A Battle between Intersystem Crossing and Internal Conversion. https://doi.org/10.1021/acs.jpclett.5c00310

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