TY  - JOUR
A1  - Wilkin, Kyle J.
A1  - Parrish, Robert M.
A1  - Yang, Jie
A1  - Wolf, Thomas J. A.
A1  - Nunes, J. Pedro F.
A1  - Gühr, Markus
A1  - Li, Renkai
A1  - Shen, Xiaozhe
A1  - Zheng, Qiang
A1  - Wang, Xijie
A1  - Martinez, Todd J.
A1  - Centurion, Martin
T1  - Diffractive imaging of dissociation and ground-state dynamics in a complex molecule
JF  - Physical review : A, Atomic, molecular, and optical physics
N2  - We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules (C2F4I2) in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine 5p perpendicular to orbital to a mixed 5p parallel to sigma hole and CF2 center dot antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the C2F4I radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.
Y1  - 2019
U6  - https://doi.org/10.1103/PhysRevA.100.023402
SN  - 2469-9926
SN  - 2469-9934
VL  - 100
IS  - 2
PB  - American Physical Society
CY  - College Park
ER  - 
TY  - JOUR
A1  - Wolf, Thomas J. A.
A1  - Parrish, Robert M.
A1  - Myhre, Rolf H.
A1  - Martinez, Todd J.
A1  - Koch, Henrik
A1  - Gühr, Markus
T1  - Observation of Ultrafast Intersystem Crossing in Thymine by Extreme Ultraviolet Time-Resolved Photoelectron Spectroscopy
JF  - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory
N2  - We studied the photoinduced ultrafast relaxation dynamics of the nucleobase thymine using gas-phase time-resolved photoelectron spectroscopy. By employing extreme ultraviolet pulses from high harmonic generation for photoionization, we substantially extend our spectral observation window with respect to previous studies. This enables us to follow relaxation of the excited state population all the way to low-lying electronic states including the ground state. In thymine, we observe relaxation from the optically bright (1)pi pi* state of thymine to a dark (1)n pi* state within 80 +/- 30 fs. The (1)n pi* state relaxes further within 3.5 +/- 0.3 ps to a low-lying electronic state. By comparison with quantum chemical simulations, we can unambiguously assign its spectroscopic signature to the (3)pi pi* state. Hence, our study draws a comprehensive picture of the relaxation mechanism of thymine including ultrafast intersystem crossing to the triplet manifold.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpca.9b05573
SN  - 1089-5639
SN  - 1520-5215
VL  - 123
IS  - 32
SP  - 6897
EP  - 6903
PB  - American Chemical Society
CY  - Washington
ER  -