Accidental triplet harvesting in donor-acceptor dyads with low spin-orbit coupling.

We present an accidental mechanism for efficient intersystem crossing (ISC) between singlet and triplet states with low spin-orbit coupling (SOC) in molecules having donor-acceptor (D-A) moieties separated by a Sigma bond. Our study shows that SOC between the lowest singlet excited state and the higher-lying triplet states, together with nuclear motion-driven coupling of this triplet state with lower-lying triplet states during the free rotation about a Sigma bond, is one of the possible ways to achieve the experimentally observed ISC rate for a class of D-A type photoredox catalysts. This mechanism is found to be the dominant contributor to the ISC process with the corresponding rate reaching a maximum at a dihedral angle in the range of 72°-78° between the D-A moieties of 10-(naphthalen-1-yl)-3,7-diphenyl-10H-phenoxazine and other molecules included in the study. We have further demonstrated that the same mechanism is operative in a specific spirobis[anthracene]dione molecule, where the D and A moieties are interlocked near to the optimal dihedral angle, indicating the plausible effectiveness of the proposed mechanism. The present finding is expected to have implications in strategies for the synthesis of new generations of triplet-harvesting organic molecules.

Photophysics of uracil: an explicit time-dependent generating function-based method combining both nonadiabatic and spin-orbit coupling effects.

We present a composite framework for calculating the rates of non-radiative deactivation processes, namely internal conversion (IC) and intersystem crossing (ISC), on an equal footing by explicitly computing the non-adiabatic coupling (NAC) and spin-orbit coupling (SOC) constants, respectively. The stationary-state approach uses a time-dependent generating function based on Fermi's golden rule. We validate the applicability of the framework by computing the rate of IC for azulene, obtaining comparable rates to experimental and previous theoretical results. Next, we investigate the photophysics associated with the complex photodynamics of the uracil molecule. Interestingly, our simulated rates corroborate experimental observations. Detailed analyses using Duschinsky rotation matrices, displacement vectors and NAC matrix elements are presented to interpret the findings alongside testing the suitability of the approach for such molecular systems. The suitability of the Fermi's golden rule based method is explained qualitatively in terms of single-mode potential energy surfaces.

Spin-vibronic interaction induced reverse intersystem crossing: A case study with TXO-TPA and TXO-PhCz molecules.

We highlight the important roles the direct spin-orbit (DSO) coupling, the spin-vibronic (SV) coupling, and the dielectric constant of the medium play on the reverse intersystem crossing (RISC) mechanism of TXO-TPA and TXO-PhCz molecules. To understand this complex phenomenon, we have calculated the RISC rate constant, kRISC, using a time-dependent correlation function-based method within the framework of second-order perturbation theory. Our computed kRISC in two different solvents, toluene and chloroform, suggests that in addition to the DSO, a dielectric medium-dependent SV mechanism may also have a significant impact on the net enhancement of the rate of RISC from the lowest triplet state to the first excited singlet state. Whereas we have found that kRISC of TXO-TPA is mostly determined by the DSO contribution independent of the choice of the solvent, the SV mechanism contributes more than 30% to the overall kRISC of TXO-PhCz in chloroform. In toluene, however, the SV mechanism is less important for the RISC process of TXO-PhCz. An analysis of mode-specific nonadiabatic coupling (NAC) between T2 and T1 of TXO-PhCz and TXO-TPA suggests that the NAC values in certain normal modes of TXO-PhCz are much higher than those of TXO-TPA, and it is more pronounced with chloroform as a solvent. The findings demonstrate the role of the solvent-assisted SV mechanism toward the net RISC rate constant, which in turn maximizes the efficiency of thermally activated delayed fluorescence.

Behind the scenes of spin-forbidden decay pathways in transition metal complexes.

The interpretation of the ultrafast photophysics of transition metal complexes following photo-absorption is quite involved as the heavy metal center leads to a complicated and entangled singlet-triplet manifold. This opens up multiple pathways for deactivation, often with competitive rates. As a result, intersystem crossing (ISC) and phosphorescence are commonly observed in transition metal complexes. A detailed understanding of such an excited-state structure and dynamics calls for state-of-the-art experimental and theoretical methodologies. In this review, we delve into the inability of non-relativistic quantum theory to describe spin-forbidden transitions, which can be overcome by taking into account spin-orbit coupling, whose importance grows with increasing atomic number. We present the quantum chemical theory of phosphorescence and ISC together with illustrative examples. Finally, a few applications are highlighted, bridging the gap between theoretical studies and experimental applications, such as photofunctional materials.

The influence of spin-orbit coupling, Duschinsky rotation and displacement vector on the rate of intersystem crossing of benzophenone and its fused analog fluorenone: a time dependent correlation function based approach.

To understand the effect of structural rigidity or flexibility on the intersystem crossing rate, herein we have adopted a time dependent correlation function based approach, an appropriate method for a harmonic oscillator under Condon approximation. Following this technique, we have developed generalized codes for calculating the rate of intersystem crossing (ISC) both at 0 K and at finite temperature. Since the rate of ISC is a measurable quantity, we have separated the real and imaginary parts of the complex correlation function carefully and eliminated the imaginary part by exploiting the odd nature of this function. Using this simplified method, we have calculated the ISC rate constant (kISC) of two molecules, namely, benzophenone and its fused analog, fluorenone. The calculations clearly elucidate that kISC of benzophenone is 103 times larger compared to that of fluorenone. Interestingly, our analyses reveal that the combined effect of spin-orbit coupling and the number of normal modes could increase the rate of ISC of benzophenone by three orders in comparison to that of fluorenone. Furthermore, the Duschinsky rotation matrix (J) and displacement vectors (D) could influence the rate of ISC by one order each, indicating that the overall rate of ISC of benzophenone could have been 105 times higher than that of fluorenone if the latter two factors, namely, J and D have practically no impact on the rate of ISC of fluorenone. However, it has been found that albeit J can't alter the rate of ISC of fluorenone, D indeed can change the rate by two orders, thereby keeping the overall ratio of the rate of ISC of benzophenone and fluorenone as 103. The present study elucidates that none of the above mentioned factors alone can explain the relative rate of ISC of the studied systems; rather a complex interplay between all these factors makes the rate of ISC of benzophenone 103 times higher than that of fluorenone.

Reverse Intersystem Crossing Dynamics in Vibronically Modulated Inverted Singlet-Triplet Gap System: A Wigner Phase Space Study.

We inspect the origin of the inverted singlet-triplet gap (INVEST) and slow change in the reverse intersystem crossing (rISC) rate with temperature, as recently observed. A Wigner phase space study reveals that, though INVEST is found at equilibrium geometry, variation in the exchange interaction and the doubles-excitation for other geometries in the harmonic region leads to non-INVEST behavior. This highlights the importance of nuclear degrees of freedom for the INVEST phenomenon, and in this case, geometric puckering of the studied molecule determines INVEST and the associated rISC dynamics.

Demystifying the Origin of Vibrational Coherence Transfer Between the S1 and T1 States of the Pt-pop Complex.

We demonstrate that spin-vibronic coupling is the most significant mechanism in vibrational coherence transfer (VCT) from the singlet (S1) to the triplet (T1) state of the [Pt2(P2O5H2)4]4- complex. Our time-dependent correlation function-based study shows that the rate of intersystem crossing (kISC) through direct spin-orbit coupling is negligibly small, making VCT vanishingly small due to the ultrashort decoherence time (2.5 ps). However, the inclusion of the spin-vibronic contribution to the net kISC in selective normal modes along the Pt-Pt axis increases the kISC to such an extent that VCT becomes feasible. Our results suggest that kISC for the S1 →T2 (τISC = 1.084 ps) is much faster than the S1 → T1 (τISC = 763.4 ps) and S1 → T3 (τISC = 13.38 ps) in CH3CN solvent, indicating that VCT is possible from the low-lying excited singlet (S1) to the triplet (T1) state through the intermediate T2 state. This is the first example where VCT occurs solely due to spin-vibronic interactions. This finding can pave the way for new types of photocatalysis.