Table 3.

Calculated (for methyl Chl-a) and observed (for Chl-a) reorganization energies (in cm⁻¹) for y-polarized Franck-Condon allowed Q_y absorption (λ^A) and emission (λ^E), compared to analogous results for Pheo-a (Rätsep et al., 2019b) and BChl-a (Rätsep et al., 2011).

Method	Mg Coord.	Pheo-a		BChl-a		Chl-a
		λA	λE	λA	λE	λA	λE
Obs.j1 4.5 K TEA ΔFLN and SEF	-	317	395
Obs.j1 low res. 4.5 K TEA	-	355	402
Obs.j2 1.7 K EtOH/MeOH low res. MCD	-	424
Obs.j3 4 K TEA ΔFLN	6				219
Obs.j3,j4 5 K HB	5			378
Obs.j3 295 K TEA	5			335	185
Obs.j3 4.5 K TEA low res.	6			196	236
Obs.j3 4.5 K TEA low res.	−5	-	-	335	260
Obs. 5 K TEA, low res.	5					~300h	458
Obs. 5 K TEA, ΔFLN	5						370
Obs. 295 K TEA, low res.	5						413
Obs.j2 4 K wet ether FE	5f					262e
Obs. 295 K wet ether, low res.	5					264i	438
Obs.j5 4 K 1-propanol ΔFLN	6						650
Obs.j2 4 K 1-propanol low res.	6					~420b	~650a
Obs.j5 295 K 1-propanol low res.	5					~490c	492
Obs.j2,j6 PS-I-200 HB	5					547g
Obs.j2,j7 WSCP HB	5					645g
CAM-B3LYP/6-31G* from calc. energies	4	1,214d,j1	481j1	350j3	210j3	607j2	517j2
CAM-B3LYP/6-31G* from scaled frequencies	4			300j3	200j3	567	492
B3LYP/6-31G* from calc. energies	4	184j1	165j1	130j3	150j3	243	245
MN15/6-31G* from calc. energies	4	493j1	282j1	184	167	390	358
ωB97XD/6-31G* from calc. energies	4	1,609d,j1	594j1	310j3	1,140j3	713	606

^aObserved spectrum (Rätsep et al., 2009a) is deconvoluted (see Figure 5) into two bands representing the dominant 6-coordinate species (85%) and a secondary 5-coordinate one using the spectral bandshape from ΔFLN, indicating that the ΔFLN results accurately depict traditional low-resolution data.

^bObserved absorption and MCD spectra are fitted to a model depicting 85% 6-coordinate species, scaling the bandshape observed in wet ether by FE (see Figure 6) (Reimers et al., 2013).

^cVery crude estimate for the 5-coordinate species assuming that the x polarized absorption commences is located 1,000 cm^-1 above Q_x origin and has the same intensity as that observed for the 6-coordinate species.

^dOne poorly represented mode depicting aromaticity in Q_y involving interactions with nitrogen lone-pair orbitals; neglecting this results become CAM-B3LYP 465 cm^-1, ωB97XD 475 cm⁻¹.

^eAfter removal of Q_x using full-quantum spectral simulations (Reimers et al., 2013).

^fLigand is water (Reimers et al., 2014).

^gFrom hole-burning (HB) data, but qualitatively unreliable owing to baseline uncertainties (Reimers et al., 2013).

^hAfter approximate removal of Q_x band using the bandshape deduced in wet ether (Reimers et al., 2013).

ⁱFrom analytical inversion (Reimers and Krausz, 2014) of absorption and MCD data (Umetsu et al., 1999).

^jReferences: 1- (Rätsep et al., 2019b), 2- (Reimers et al., 2013), 3- (Rätsep et al., 2011), 4- (Zazubovich et al., 2001), 5- (Rätsep et al., 2009a), 6- (Gillie et al., 1989), 7- (Hughes et al., 2010).