Theoretical and REMPI spectroscopic study on phenylhydrazine and phenylhydrazine-(Ar)n (n=1, 2) van der Waals complexes.
Phenylhydrazine and its van der Waals complexes with one or two argon atoms were investigated with theoretical calculations and resonant two photon ionization (R2PI) spectroscopy. The ab initio and DFT calculations found a conversion of the orbital hybridization of the Nbeta atom from sp3-like in the S0 state to sp2-like in the S1 state, suggesting that the lone pair electrons of the Nbeta atom are involved in a super p-p-pi conjugation over the skeleton of phenylhydrazine in the S1 state. The structural change of the hydrazino group in the S1<--S0 electronic transition was reflected by the vibrational excitations of the hydrazino group observed in the 1C-R2PI spectrum. The band origin of the S1<--S0 transition is determined to be 33610 cm(-1) and the adiabatic ionization energy (IE) of phenylhydrazine, measured by 2C-R2PI spectroscopy, is 62829+/-15 cm(-1). The S1<--S0 electronic transitions of phenylhydrazine-Ar and phenylhydrazine-Ar2 complexes were also observed in the 1C-R2PI spectrum, and their band origins are, respectively, red-shifted by 39 and 80 cm(-1) from that of phenylhydrazine.
Xiao
Daoqing
D
The State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR China.
Yu
Dan
D
Xu
Xiling
X
Yu
Zijun
Z
Cheng
Min
M
Du
Yikui
Y
Zheng
Weijun
W
Zhu
Qihe
Q
Zhang
Cunhao
C