Time-Resolved Photoelectron Spectroscopy of Dissociating 1,2-Butadiene Molecules by High Harmonic Pulses.
Using 42 nm high harmonic pulses, the dissociation dynamics of 1,2-butadiene was investigated by time-resolved photoelectron spectroscopy (TRPES), enabling us to observe dynamical changes of multiple molecular orbitals (MOs) with higher temporal resolution than conventional light sources. Because each lower-lying occupied MO has particular spatial electron distribution, the structural dynamics of photochemical reaction can be revealed. On the femtosecond time scale, a short-lived excited state with a lifetime of 37 ± 15 fs and the coherent oscillation of the photoelectron yield stimulated by Hertzberg-Teller coupling were observed. Ab initio molecular dynamics simulations in the electronically excited state find three relaxation pathways from the vertically excited structure in S1 to the ground state, and one of them is the dominant relaxation pathway, observed as the short-lived excited state. On the picosecond time scale, the photoelectron yields related to the C-C bond decreased upon photoexcitation, indicating C-C bond cleavage.
†Department of Applied Physics, Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628, Japan.
Ryo
R
Iikubo
†Department of Applied Physics, Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628, Japan.
Takehisa
T
Fujiwara
†Department of Applied Physics, Faculty of Engineering, Hokkaido University, Kita 13 Nishi 8, Kita-ku, Sapporo 060-8628, Japan.
Taro
T
Sekikawa
‡Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo 060-0810, Japan.
Yu
Y
Harabuchi
‡Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo 060-0810, Japan.
Sota
S
Satoh
‡Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo 060-0810, Japan.
Tetsuya
T
Taketsugu
§Materials and Structures Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.
Yosuke
Y
Kayanuma
D002070:Butadienes / Q000737:chemistry*; D004583:Electrons; D056004:Molecular Dynamics Simulation / Q000706:statistics & numerical data*; D056951:Photoelectron Spectroscopy / Q000379:methods*; D011674:Pulse; D013997:Time Factors
D002070:Butadienes; C031763:1,3-butadiene
ab initio molecular dynamics; conical intersection; dissociation; high harmonics; photoelectron spectroscopy