Table 4. Emission Energies of the matched and mismatched duplexes.

Vertical Emission Energies (VEE) and oscillator strengths (f) at the QM(PCM/M052X/6–31G(d) Linear Response (LR) level of theory are compared to those computed at the State Specific (SS)-PCM. Charge Transfer character (CT in a.u), radiative lifetime (τ_R in ns) and computed fluorescence lifetimes (^c<τ> in ns) of the different minima for the different duplexes.

	(−)PBS	(+)PBS	Description.	LRVEE (eV)	LRf	LRCT	SSVEE (eV)	SSf	SSτR	c<τ>
Match	AthGA	TCT	Min-ππ*	3.28	0.07	0.03	3.20	0.05	74	13.4
			Min-CT (thG→A)	3.77	0.01	0.58	2.53	0.00
	TthGT	ACA	Min-ππ*modell	3.43	0.08	0.01	3.32	0.05	64	9.7
			Min-CTmodel2 (thG→T)	3.34	0.00	0.86	1.68	0.00
	CthGC	GCG	Min-ππ*	3.42	0.08	0.01	3.33	0.06	52	8.3
			Min-CT (thG→C)	a3.88	0.03	0.72	2.10	0.01
	GthGG	CCC	Min-ππ*	3.47	0.08	0.03	3.33	0.05	64	9.6
			Min-CT (G→thG)	3.15	0.02	−0.22	2.80	0.01
Mismatched	GthGG	CTC	Min-ππ*	b
			Min-CT (G→thG)	4.24	0.07	−0.22	2.91	0.01	7000
	AthGA	TAT	Min-ππ*	3.67	0.11	0.03	3.39	0.08	29	14.0
			Min-CT	c
	TthGT	ATA	g1Min-ππ*	3.46	0.07	0.04	3.32	0.05	68	23.7
			g1Min-ct (thG→T)	3.36	0.06	0.06	3.24	0.04
	TthGT	AAA	g3Min-ππ*	3.50	0.08	0.01	3.29	0.06	62	22.8
			g1Min-ct (thG→T)	2.93	0.01	0.16	2.80	0.01
	TthGT	AGA	Min-ππ*	3.63	0.11	0.00	3.33	0.08	28	2.8
			Min-CT	c
thG+water			Min-ππ*	3.60	0.11	-	3.22	0.08	31	15.8
thG+2H2O			Min-ππ*	3.45	0.11	-	3.15	0.08	31	15. 8

Notes: a) No real minimum but a low energy gradient region was found, b) no clear ππ * minimum was found, c) no clear CT minimum was located. The radiative lifetime (τ_R) was estimated by using a simplified version of the Strickler-Berg formula: ${}^{\text{Theor}}{\tau }_{\text{R}}=\frac{1}{{\text{k}}_{\text{R}}}$ with ${\text{k}}_{\text{R}}=\frac{4\Delta {\text{E}}^3}{3{\text{c}}^3}{\mu }^2$, where ΔE is the vertical emission energy and the dipole moment of the transition. The computed lifetime is calculated by: ^c<τ> = k_R×QY, where QY is the experimental quantum yield. Further details on the calculations are given in section 4 of SI.