TY - JOUR
T1 - Conical-Intersection Topographies Suggest That Ribose Exhibits Enhanced UV Photostability
AU - Tuna, Deniz
AU - Sobolewski, Andrzej L.
AU - Domcke, Wolfgang
N1 - Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/10/20
Y1 - 2016/10/20
N2 - Carbohydrates are essential building blocks of life that assume a multitude of biological functions in all living organisms found on Earth. It was recently reported that ribose was identified in UV-irradiated interstellar ice analogs, which suggests that it can be found on comets and that it may have been transported to Earth via the impact of comets. Herein, we present computational results obtained with multiconfigurational ab initio quantum-chemical methods showing that various photochemical processes for radiationless deactivation are available for photoexcited ribose. These processes are driven by nσ∗ states and involve either O-H- or endocyclic or exocyclic C-O-bond elongation whereby a conical intersection with the electronic ground state becomes accessible. The local topography of the potential-energy surfaces around these conical intersections suggests that these intersections mediate efficient radiationless deactivation and favor regeneration of the initially photoexcited ground-state reactant. These findings indicate that ribose found in interstellar space can be expected to be highly photostable upon irradiation with UV starlight, which could be of relevance in the field of astrobiology.
AB - Carbohydrates are essential building blocks of life that assume a multitude of biological functions in all living organisms found on Earth. It was recently reported that ribose was identified in UV-irradiated interstellar ice analogs, which suggests that it can be found on comets and that it may have been transported to Earth via the impact of comets. Herein, we present computational results obtained with multiconfigurational ab initio quantum-chemical methods showing that various photochemical processes for radiationless deactivation are available for photoexcited ribose. These processes are driven by nσ∗ states and involve either O-H- or endocyclic or exocyclic C-O-bond elongation whereby a conical intersection with the electronic ground state becomes accessible. The local topography of the potential-energy surfaces around these conical intersections suggests that these intersections mediate efficient radiationless deactivation and favor regeneration of the initially photoexcited ground-state reactant. These findings indicate that ribose found in interstellar space can be expected to be highly photostable upon irradiation with UV starlight, which could be of relevance in the field of astrobiology.
UR - http://www.scopus.com/inward/record.url?scp=84992381797&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcb.6b09048
DO - 10.1021/acs.jpcb.6b09048
M3 - Article
AN - SCOPUS:84992381797
SN - 1520-6106
VL - 120
SP - 10729
EP - 10735
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 41
ER -