2 research outputs found
Photoelectrochromism in the Retinal Protonated Schiff Base Chromophore: Photoisomerization Speed and Selectivity under a Homogeneous Electric Field at Different Operational Regimes
No full textThe
spectral tunability, photoisomerization efficiency and selectivity,
of the native all-trans retinal protonated Shiff base (PSB) chromophore
driven by a homogeneous electric field is systematically investigated.
By analyzing the absorption wavelength dependence, charge distribution,
and PES profiles along selected torsional angles, as well as the electronic
structure, energetics, and topography of the CI seam in the presence
of strong positive and negative electric fields, we recognize the
existence of qualitatively/fundamentally different photophysics and
photochemistry with respect to the unperturbed (i.e., absence of an
electric field) chromophore. We rationalize the findings within the
scope of molecular orbital theory and deliver a unified picture of
the photophysics of the retinal PSB chromophore over a wide, even
beyond the usually observed, spectral regime, ranging from the near-infrared
to the ultraviolet absorption energies. This work has a 3-fold impact:
a) it accounts for, and extends, previous theoretical studies on the
subject; b) it delivers a rationale for the ES lifetimes observed
in retinal proteins, both archeal and visual rhodopsins, as well as
in solvent; and c) the transferability of the discovered trends on
PSB mimics is demonstrated
Photoelectrochromism in the Retinal Protonated Schiff Base Chromophore: Photoisomerization Speed and Selectivity under a Homogeneous Electric Field at Different Operational Regimes
No full textThe
spectral tunability, photoisomerization efficiency and selectivity,
of the native all-trans retinal protonated Shiff base (PSB) chromophore
driven by a homogeneous electric field is systematically investigated.
By analyzing the absorption wavelength dependence, charge distribution,
and PES profiles along selected torsional angles, as well as the electronic
structure, energetics, and topography of the CI seam in the presence
of strong positive and negative electric fields, we recognize the
existence of qualitatively/fundamentally different photophysics and
photochemistry with respect to the unperturbed (i.e., absence of an
electric field) chromophore. We rationalize the findings within the
scope of molecular orbital theory and deliver a unified picture of
the photophysics of the retinal PSB chromophore over a wide, even
beyond the usually observed, spectral regime, ranging from the near-infrared
to the ultraviolet absorption energies. This work has a 3-fold impact:
a) it accounts for, and extends, previous theoretical studies on the
subject; b) it delivers a rationale for the ES lifetimes observed
in retinal proteins, both archeal and visual rhodopsins, as well as
in solvent; and c) the transferability of the discovered trends on
PSB mimics is demonstrated
