1 3
Top Curr Chem (Z) (2018) 376:10
alone has a meaningless lineshape due to an artifact known as phase twist [1, 43, 56,
57]. It is important to probe the ellipticity on the 2DES maps of the absorptive signal, i.e., after summing the rephasing and non-rephasing signals.
Due to the high degree of information contained within 2DES maps, it was possible to resolve a controversy that lasted for years in the literature. The photoisomerization of P r isomer of the phytochrome Cph1 involves one homogeneous ground
state. The photoisomerization takes place in the excited state. 2DES shows how it
is easy to unravel this mechanism, which was impossible to interpret from 1D data.
The third example demonstrates how 2DES measurements can reveal insights into
spectra that are completely dominated by inhomogeneous broadening. In this case,
measuring non-rephasing and rephasing signals was crucial. It is a study on cubic
CdSe nanocrystals where the nanocrystal size variation makes this system highly
heterogeneous (Fig. 7) [12]. CdSe nanocrystals have applications in photovoltaics
Fig. 7 a Representation of colloidal cadmium selenide (CdSe) nanocrystals in cubic phase. b Steadystate absorption spectrum of CdSe nanocrystals in toluene (line) and the excitation laser spectrum (dash).
c Rephasing, non-rephasing and absorptive 2DES map in magnitudes of CdSe nanocrystals at a waiting
time of 120 fs. Adapted with permission from [12]. Copyright 2012 American Chemical Society
37
Reprinted from the journal
Top Curr Chem (Z) (2018) 376:10
alone has a meaningless lineshape due to an artifact known as phase twist [1, 43, 56,
57]. It is important to probe the ellipticity on the 2DES maps of the absorptive signal, i.e., after summing the rephasing and non-rephasing signals.
Due to the high degree of information contained within 2DES maps, it was possible to resolve a controversy that lasted for years in the literature. The photoisomerization of P r isomer of the phytochrome Cph1 involves one homogeneous ground
state. The photoisomerization takes place in the excited state. 2DES shows how it
is easy to unravel this mechanism, which was impossible to interpret from 1D data.
The third example demonstrates how 2DES measurements can reveal insights into
spectra that are completely dominated by inhomogeneous broadening. In this case,
measuring non-rephasing and rephasing signals was crucial. It is a study on cubic
CdSe nanocrystals where the nanocrystal size variation makes this system highly
heterogeneous (Fig. 7) [12]. CdSe nanocrystals have applications in photovoltaics
Fig. 7 a Representation of colloidal cadmium selenide (CdSe) nanocrystals in cubic phase. b Steadystate absorption spectrum of CdSe nanocrystals in toluene (line) and the excitation laser spectrum (dash).
c Rephasing, non-rephasing and absorptive 2DES map in magnitudes of CdSe nanocrystals at a waiting
time of 120 fs. Adapted with permission from [12]. Copyright 2012 American Chemical Society
37
Reprinted from the journal