TY  - JOUR
A1  - Wolf, Thomas J. A.
A1  - Sanchez, David M.
A1  - Yang, J.
A1  - Parrish, R. M.
A1  - Nunes, J. P. F.
A1  - Centurion, M.
A1  - Coffee, R.
A1  - Cryan, J. P.
A1  - Gühr, Markus
A1  - Hegazy, Kareem
A1  - Kirrander, Adam
A1  - Li, R. K.
A1  - Ruddock, J.
A1  - Shen, Xiaozhe
A1  - Vecchione, T.
A1  - Weathersby, S. P.
A1  - Weber, Peter M.
A1  - Wilkin, K.
A1  - Yong, Haiwang
A1  - Zheng, Q.
A1  - Wang, X. J.
A1  - Minitti, Michael P.
A1  - Martinez, Todd J.
T1  - The photochemical ring-opening of 1,3-cyclohexadiene imaged by ultrafast electron diffraction
JF  - Nature chemistry
N2  - The ultrafast photoinduced ring-opening of 1,3-cyclohexadiene constitutes a textbook example of electrocyclic reactions in organic chemistry and a model for photobiological reactions in vitamin D synthesis. Although the relaxation from the photoexcited electronic state during the ring-opening has been investigated in numerous studies, the accompanying changes in atomic distance have not been resolved. Here we present a direct and unambiguous observation of the ring-opening reaction path on the femtosecond timescale and subangstrom length scale using megaelectronvolt ultrafast electron diffraction. We followed the carbon-carbon bond dissociation and the structural opening of the 1,3-cyclohexadiene ring by the direct measurement of time-dependent changes in the distribution of interatomic distances. We observed a substantial acceleration of the ring-opening motion after internal conversion to the ground state due to a steepening of the electronic potential gradient towards the product minima. The ring-opening motion transforms into rotation of the terminal ethylene groups in the photoproduct 1,3,5-hexatriene on the subpicosecond timescale.
KW  - Organic chemistry
KW  - Photochemistry
KW  - Physical chemistry
KW  - Theoretical chemistry
Y1  - 2019
U6  - https://doi.org/10.1038/s41557-019-0252-7
SN  - 1755-4330
SN  - 1755-4349
VL  - 11
IS  - 6
SP  - 504
EP  - 509
PB  - Nature Publ. Group
CY  - London
ER  - 
TY  - JOUR
A1  - Yang, Jie
A1  - Zhu, Xiaolei
A1  - Wolf, Thomas J. A.
A1  - Li, Zheng
A1  - Nunes, João Pedro Figueira
A1  - Coffee, Ryan
A1  - Cryan, James P.
A1  - Gühr, Markus
A1  - Hegazy, Kareem
A1  - Heinz, Tony F.
A1  - Jobe, Keith
A1  - Li, Renkai
A1  - Shen, Xiaozhe
A1  - Veccione, Theodore
A1  - Weathersby, Stephen
A1  - Wilkin, Kyle J.
A1  - Yoneda, Charles
A1  - Zheng, Qiang
A1  - Martinez, Todd J.
A1  - Centurion, Martin
A1  - Wang, Xijie
T1  - Imaging CF3I conical intersection and photodissociation dynamics with ultrafast electron diffraction
JF  - Science
N2  - Conical intersections play a critical role in excited-state dynamics of polyatomic molecules because they govern the reaction pathways of many nonadiabatic processes. However, ultrafast probes have lacked sufficient spatial resolution to image wave-packet trajectories through these intersections directly. Here, we present the simultaneous experimental characterization of one-photon and two-photon excitation channels in isolated CF3I molecules using ultrafast gas-phase electron diffraction. In the two-photon channel, we have mapped out the real-space trajectories of a coherent nuclear wave packet, which bifurcates onto two potential energy surfaces when passing through a conical intersection. In the one-photon channel, we have resolved excitation of both the umbrella and the breathing vibrational modes in the CF3 fragment in multiple nuclear dimensions. These findings benchmark and validate ab initio nonadiabatic dynamics calculations.
Y1  - 2018
U6  - https://doi.org/10.1126/science.aat0049
SN  - 0036-8075
SN  - 1095-9203
VL  - 361
IS  - 6397
SP  - 64
EP  - 67
PB  - American Assoc. for the Advancement of Science
CY  - Washington
ER  - 
TY  - JOUR
A1  - Yang, Jie
A1  - Guehr, Markus
A1  - Shen, Xiaozhe
A1  - Li, Renkai
A1  - Vecchione, Theodore
A1  - Coffee, Ryan
A1  - Corbett, Jeff
A1  - Fry, Alan
A1  - Hartmann, Nick
A1  - Hast, Carsten
A1  - Hegazy, Kareem
A1  - Jobe, Keith
A1  - Makasyuk, Igor
A1  - Robinson, Joseph
A1  - Robinson, Matthew Scott
A1  - Vetter, Sharon
A1  - Weathersby, Stephen
A1  - Yoneda, Charles
A1  - Wang, Xijie
A1  - Centurion, Martin
T1  - Diffractive Imaging of Coherent Nuclear Motion in Isolated Molecules
JF  - Physical review letters
N2  - Observing the motion of the nuclear wave packets during a molecular reaction, in both space and time, is crucial for understanding and controlling the outcome of photoinduced chemical reactions. We have imaged the motion of a vibrational wave packet in isolated iodine molecules using ultrafast electron diffraction with relativistic electrons. The time-varying interatomic distance was measured with a precision 0.07 angstrom and temporal resolution of 230 fs full width at half maximum. The method is not only sensitive to the position but also the shape of the nuclear wave packet.
Y1  - 2016
U6  - https://doi.org/10.1103/PhysRevLett.117.153002
SN  - 0031-9007
SN  - 1079-7114
VL  - 117
PB  - American Physical Society
CY  - College Park
ER  -