Research output: Contribution to journal › Article › peer-review
Photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) via charge-transfer state : A velocity map imaging investigation. / Bogomolov, Alexandr S.; Goldort, Veniamin G.; Kochubei, Sergei A. et al.
In: Journal of Chemical Physics, Vol. 147, No. 23, 234304, 21.12.2017, p. 234304.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) via charge-transfer state
T2 - A velocity map imaging investigation
AU - Bogomolov, Alexandr S.
AU - Goldort, Veniamin G.
AU - Kochubei, Sergei A.
AU - Baklanov, Alexey V.
PY - 2017/12/21
Y1 - 2017/12/21
N2 - The photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) excited via Charge-Transfer (CT) band has been studied with the velocity map imaging technique. Photodissociation of both complexes gives rise to translationally "hot" molecular iodine I2 via channels differing by kinetic energy and angular distribution of the recoil directions. These measured characteristics together with the analysis of the model potential energy surface for these complexes allow us to infer the back-electron-transfer (BET) in the CT state to be a source of observed photodissociation channels and to make conclusions on the location of conical intersections where the BET process takes place. The BET process is concluded to provide an I2 molecule in the electronic ground state with moderate vibrational excitation as well as X molecule in the electronic excited state. In the case of X = I2, the BET process converts anion I2- of the CT state into the neutral I2 in the repulsive excited electronic state which then dissociates promptly giving rise to a pair of I atoms in the fine states 2P1/2. In the case of C2H4-I2, the C2H4 molecules appear in the triplet T1 electronic state. Conical intersection for corresponding BET process becomes energetically accessible after partial twisting of C2H4+ frame in the excited CT state of complex. The C2H4(T)-I2 complex gives rise to triplet ethylene as well as singlet ethylene via the T-S conversion.
AB - The photodissociation of van der Waals complexes of iodine X-I2 (X = I2, C2H4) excited via Charge-Transfer (CT) band has been studied with the velocity map imaging technique. Photodissociation of both complexes gives rise to translationally "hot" molecular iodine I2 via channels differing by kinetic energy and angular distribution of the recoil directions. These measured characteristics together with the analysis of the model potential energy surface for these complexes allow us to infer the back-electron-transfer (BET) in the CT state to be a source of observed photodissociation channels and to make conclusions on the location of conical intersections where the BET process takes place. The BET process is concluded to provide an I2 molecule in the electronic ground state with moderate vibrational excitation as well as X molecule in the electronic excited state. In the case of X = I2, the BET process converts anion I2- of the CT state into the neutral I2 in the repulsive excited electronic state which then dissociates promptly giving rise to a pair of I atoms in the fine states 2P1/2. In the case of C2H4-I2, the C2H4 molecules appear in the triplet T1 electronic state. Conical intersection for corresponding BET process becomes energetically accessible after partial twisting of C2H4+ frame in the excited CT state of complex. The C2H4(T)-I2 complex gives rise to triplet ethylene as well as singlet ethylene via the T-S conversion.
KW - MOLECULAR-COMPLEXES
KW - GROUND-STATE
KW - DYNAMICS
KW - SPECTROSCOPY
KW - ETHYLENE
KW - PHOTOELECTRON
KW - C6H6-I-2
KW - BENZENE
KW - OXYGEN
UR - http://www.scopus.com/inward/record.url?scp=85038931508&partnerID=8YFLogxK
U2 - 10.1063/1.5001104
DO - 10.1063/1.5001104
M3 - Article
C2 - 29272931
AN - SCOPUS:85038931508
VL - 147
SP - 234304
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 23
M1 - 234304
ER -
ID: 9400377