Unconventional two-step spin relaxation dynamics of [Re(CO)₃(im)(phen)]⁺ in aqueous solution

Abstract

Full-dimensional excited-state dynamics simulations including explicit solvation show an unprecedented two-step intersystem crossing mechanism with electronic- and nuclear-driven components in [Re(CO)3(imidazole)(phenanthroline)]+.

Competing ultrafast photoinduced electron transfer and intersystem crossing of [Re(CO)$$_3$$(Dmp)(His124)(Trp122)]$$^+$$ in Pseudomonas aeruginosa azurin: a nonadiabatic dynamics study

“…We find that, initially, the singlet population decays with a time constant of approximately 10 ± 4 fs. This result is in very good agreement with the 8 fs time constant found previously in SHARC simulations of the "small system" [Re(CO) 3 (imidazole)(phenanthroline)] + in water [22]. This very fast ISC process is due to the strong SOCs in the Re complex, which leads to the formation of a spin-orbit wave (a) (b) Fig.…”

“…From these 1000 calculations, we generated an absorption spectrum of the system. The initial excited states were determined stochastically based on the oscillator strengths [50] in the energy window 2.8-3.2 eV, the same that was used previously in the ab initio SHARC dynamics simulations of the small system [22]. The stochastic algorithm selected 200 initial conditions, where 6 started in S 1 , 36 in S 2 , 58 in S 3 , 52 in S 4 , 35 in S 5 , 8 in S 6 , 4 in S 7 , and 1 in S 8 (all in the MCH representation).…”

“…The ultrafast dynamics of the small system (shown in Fig. 1c) was studied in detail with quantum chemistry [14][15][16], quantum dynamics [17][18][19], model-potentialbased surface hopping [20], or QM/MM-based surface hopping [16,[21][22][23]. These studies have firmly established the importance of the environment effects on the In contrast to the small system, the photocycle of the medium and large systems-both of which include the Trp amino acid-has been investigated to a much smaller extent.…”

TheoDORE: A toolbox for a detailed and automated analysis of electronic excited state computations

“…For example one can study how different substitution patterns affect the excited-state wavefunctions and correlate the results to the property of interest, e.g., singlet-triplet gaps or two-photon strengths, 41,57 and use this information in a rational design process. Alternatively, TheoDORE can be used to gain detailed insight into the dynamical behaviour of a system 49,50 or to perform statistical sampling over complex molecular systems such as DNA. 39,40 It should not be left without saying that the fragment-based scheme also has some drawbacks.…”

“…If larger data sets are of interest one can, of course, skip the visualisation process altogether and directly proceed to a statistical analysis, which is particularly useful when studying an ensemble 39,40 or when performing dynamics simulations. 49,50 Whereas the Ω-matrices provide a very compact representation of the correlated exciton, this representation may be too abstract in many cases. Therefore, a different representation has been developed, 27 which formally proceeds by modifying Eq.…”