. Author manuscript; available in PMC: 2019 Jul 24.

Published in final edited form as: J Phys Chem Lett. 2018 Jun 6;9(12):3315–3322. doi: 10.1021/acs.jpclett.8b01062

Table 1.

Computed vs. predicted QYs. The computed values are obtained by analyzing the outcome of the individual trajectories for each pigment. The predictions are given on the basis of vibrational phase rules²¹ involving the HCCH direction at the time of hopping to the GS (called “hopping event”) and the time of transition from a CT to a covalent character along the S₀ PES (called “decision event”); defined as the time when the total charge on the N-terminus has reached +0.9 e. This last event corresponds to a change in the S₀ electronic wavefunction (WF) from an antibonding to a bonding character of the reactive double bond.

model	computed QY	predicted QY
		HCCH velocity sign at
		ES→GS hopping (hopping event)	CT→covalent transition (decision event)
Rh	70% [67%]¹	78 (+8%)	69 (−1%)
sqRh	68%	64 (−4%)	66 (−2%)
hMeOp	52%	61 (+9%)	54 (+2%)

The only known experimental quantity is given in square brackets^41–42. Evidence for similarity between the QYs of Rh and sqRh has been provided⁴³.