The well-known benzophenone intersy
stem crossing from S
1(n,
*) to T
1(n,
*)
states, for which direct transitionis forbidden by El-Sayed rules, is reinve
stigated by subpicosecond time-resolved absorption spectroscopyand effective data analysis for various excitation wavelengths and solvents. Multivariate curve resolutionalternating lea
st-squares analysis is used to perform bilinear decomposition of the time-resolved spectra intopure spectra of overlapping transient species and their associated time-dependent concentrations. The resultssugge
st the implication of an intermediate (IS) in the relaxation process of the S
1 state. Therefore, a two
stepkinetic model, S
1 IS
T
1, is successfully implemented as an additional con
straint in the soft-modelingalgorithm. Although this intermediate, which has a spectrum similar to the one of T
1(n,
*)
state, could beartificially induced by vibrational relaxation, it is tentatively assigned to a hot T
1(n,
*) triplet
state. Twocharacteri
stic times are reported for the transition S
1 IS and IS
T
1, ~6.5 ps and ~10 ps respectively,without any influence of the solvent. Moreover, an excitation wavelength effect is discovered sugge
sting theparticipation of unrelaxed singlet
states in the overall process. To go further discussing the spectroscopicrelevancy of IS and to rationalize the expected involvement of the T
2(
,
*)
state, we also inve
stigate4-methoxybenzophenone. For this neighboring molecule, triplet energy level is tunable through solvent polarityand a clear correlation is e
stablished between the intermediate resolved by multivariate data analysis and thepresence of a T
2(
,
*) above the T
1(n,
*) triplet. It is therefore proposed that the benzophenone intermediatespecies is a T
1(n,
*) high vibrational level in interaction with T
2(
,
*)
state.