TY - JOUR
T1 - Chlorocyclohexane valence and Rydberg electronic excitations
AU - Bandeira, E.
AU - Kumar, Sarvesh
AU - Jones, Nykola C.
AU - Hoffmann, Søren Vrønning
AU - Bettega, Marcio H. F.
AU - Limao-Vieira, Paulo
PY - 2025
Y1 - 2025
N2 - Here we present new cross-section values of chlorocyclohexane (C6H11Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H2)4 symmetric stretching (and C-H stretching), (Formula presented), (C-H2)4 wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth’s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.
AB - Here we present new cross-section values of chlorocyclohexane (C6H11Cl) from vacuum ultraviolet (VUV) photoabsorption measurements in the photon energy range of 5.0-10.8 eV (115-248 nm). Theoretical calculations using time-dependent density functional theory (TD-DFT) have been performed to aid in the interpretation of the photoabsorption spectrum. The information from these calculations has allowed the assignment of the excited states in valence, mixed valence-Rydberg, and Rydberg transitions. The fine features in the photoabsorption bands have been assigned to (C-H2)4 symmetric stretching (and C-H stretching), (Formula presented), (C-H2)4 wagging, (Formula presented) and ring puckering/C-Cl stretching (Formula presented) modes. From the absolute cross-section values, photolysis lifetimes in the Earth’s atmosphere have been estimated, showing that solar photolysis may only be considered a relevant sink at altitudes above 20 km. Additional calculations at the TD-DFT level of theory have been performed to obtain potential energy curves for the lowest-lying electronic states, highlighting the role of predissociative character.
UR - http://www.scopus.com/inward/record.url?scp=105003069448&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.5c01122
DO - 10.1021/acs.jpca.5c01122
M3 - Journal article
SN - 1089-5639
VL - 129
SP - 3857
EP - 3866
JO - The Journal of Physical Chemistry Part A
JF - The Journal of Physical Chemistry Part A
IS - 17
ER -