Two-Photon Excited State Dynamics of Dark Rydberg and Bright Valence States in Furan
Jin-You Long, Chun-Long Hu, Bing Zhang** ,
State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071
Abstract ：Two-photon absorption in systems with parity permits access to states that cannot be directly prepared by one-photon absorption. Here we investigate ultrafast internal conversion (IC) dynamics of furan by using this strategy in combination with femtosecond time-resolved photoelectron imaging. The dark Rydberg $S_{1}$ and bright valence $S_{2}$ states are simultaneously excited by two photons of 405 nm, and then ionized by two photons of 800 nm. The IC from $S_{2}$ to $S_{1}$ is clearly observed and extracted from the time dependence of the higher photoelectron kinetic energy (PKE) component. More importantly, the internal conversions to hot $S_{0}$ from directly-prepared $S_{1}$ and secondarily-populated $S_{1}$ are unambiguously identified by the time-dependence of the lower PKE component. The average lifetime of the $S_{2}$ and $S_{1}$ states is measured to be 29 fs. The internal conversions of $S_{2}$ to $S_{1}$, $S_{1}$ to hot $S_{0 }$ occur on estimated timescales of 15.4 fs and 38 fs, respectively.
收稿日期: 2016-11-29
出版日期: 2017-03-21
:
31.70.Hq
(Time-dependent phenomena: excitation and relaxation processes, and reaction rates)
33.15.Vb
(Correlation times in molecular dynamics)
33.50.-j
(Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion))
[1] Suzuki T 2006 Annu. Rev. Phys. Chem. 57 555 [2] Stolow A 2003 Annu. Rev. Phys. Chem. 54 89 [3] Tapia A, Villanueva F, Salgado M S et al 2011 Atmos. Chem. Phys. 11 3227 [4] Román-Leshkov Y, Barrett C J, Liu Y et al 2007 Nature 447 982 [5] Picket L W 1940 J. Chem. Phys. 8 293 [6] Pickett L W, Hoeflich N J, Liu T et al 1951 J. Am. Chem. Soc. 73 4865 [7] Watanabe K and Nakayama T 1958 J. Chem. Phys. 29 48 [8] Flicker W M, Mosher O A and Kuppermann A 1976 Chem. Phys. Lett. 38 489 [9] Flicker W M, Mosher O A and Kuppermann A 1976 J. Chem. Phys. 64 1315 [10] Sanche L 1979 J. Chem. Phys. 71 4860 [11] Cooper C D, Williamson A D, Miller J C et al 1980 J. Chem. Phys. 73 1527 [12] Nyulaszi L 1992 J. Mol. Struct. 273 133 [13] Palmer M H, Walker I C, Ballard C C et al 1995 Chem. Phys. 192 111 [14] Thunemann K, Buenker R J and Butscher W 1980 Chem. Phys. 47 313 [15] Nakatsuji H, Kitao O and Yonezawa T 1985 J. Chem. Phys. 83 723 [16] Serrano-Andres L, Merchan M and Nebot-Gil I 1993 J. Am. Chem. Soc. 115 6184 [17] Nakano H, Tsuneda T and Hashimoto T 1996 J. Chem. Phys. 104 2312 [18] Trofimov A B and Schirmer J 1997 Chem. Phys. 224 175 [19] Christiansen O, Halkier A, Koch H et al 1998 J. Chem. Phys. 108 2801 [20] Christiansen O and Jørgensen P 1998 J. Am. Chem. Soc. 120 3423 [21] Wan J, Meller J, Hada M et al 2000 J. Chem. Phys. 113 7853 [22] Burcl R, Amos R D and Handy N C 2002 Chem. Phys. Lett. 355 8 [23] Gromov E V, Trofimov A B, Vitkovskaya N M et al 2003 J. Chem. Phys. 119 737 [24] Gromov E V, Trofimov A B, Vitkovskaya N M et al 2004 J. Chem. Phys. 121 4585 [25] Köppel H, Gromov E V and Trofimov A B 2004 Chem. Phys. 304 35 [26] Gavrilov N, Salzmann S and Marian C M 2008 Chem. Phys. 349 269 [27] Gromov E V, Trofimov A B, Gatti F et al 2010 J. Chem. Phys. 133 164309 [28] Humeniuk A, Wohlgemuth M, Suzuki T et al 2013 J. Chem. Phys. 139 134104 [29] Gromov E V, Reddy V S, Gatti F et al 2013 J. Chem. Phys. 139 234306 [30] Fuji T, Suzuki Y, Horio T et al 2010 J. Chem. Phys. 133 234303 [31] Spesyvtsev R, Horio T, Suzuki Y et al 2015 J. Chem. Phys. 143 014302 [32] Liu Y, Knopp G, Qin C et al 2015 Chem. Phys. 446 142 [33] Liu Y, Qin C and Zhang S 2011 Acta Phys. -Chim. Sin. 27 965 [34] Liu Y, Tang B, Shen H et al 2010 Opt. Express 18 5791 [35] Dribinski V, Ossadtchi A, Mandelshtam V A et al 2002 Rev. Sci. Instrum. 73 2634 [36] Wojdyr M 2010 J. Appl. Crystallogr. 43 1126 [37] Han K L and He G Z 2007 J. Photoch. Photobio. C 8 55 [38] Liu Y, Gerber T, Qin C et al 2016 J. Chem. Phys. 144 084201
[1]
.
[2]
.
[3]
JIN Cheng;ZHOU Xiao-Xin;ZHAO Song-Feng. Destructive and Constructive Interference of High-Order Harmonic Generation in Mixture of He and Ne Gases
[4]
WANG Fa-Qiang;LIU Wei-Ci;LIANG Rui-Sheng. Vacuum Rabi Oscillation of an Atom without Rotating-Wave Approximation
[5]
SANG Cui-Cui;DING Xiao-Bin;DONG Chen-Zhong. Photoionization of 1s Electron and Corresponding Shake-Up Process in Ground and Excited Lithium Atoms
[6]
CHEN Shao-Hao;LI Jia-Ming;. Real-Space Wave-Packet Propagation Method: Application to Photoabsorption Processes of Hydrogen Atoms
[7]
WANG Xiao-Lu;CHEN Shao-Hao;HE Chun-Long;LI Jia-Ming;. Recombination Process of Hydrogen Molecular Ions: An Application of Time-Dependent Wave Packet Dynamics Method
[8]
YUAN Kai-Jun;WANG Sen-Ming;CONG Shu-Lin. Controlling Population Transfer and Dissociation Rate of Na2 Molecules with Ultra-Short Intense Laser Pulses
[9]
LI Hao;LIU Xin-Guo;ZHANG Qing-Gang. Stereodynamics and Rovibrational Effect for H+NH3 →H2 +NH2 Reaction
[10]
CHEN Shao-Hao;HE Chun-Long;CHEN Chao;LI Jia-Ming;. Vibrational Distribution of Hydrogen Molecular Ions in High-Energy Ionization Processes
[11]
CHEN Shao-Hao;WANG Feng;LI Jia-Ming;. Theoretical Analysis of Time-Dependent Wave-Packet Dynamics: Proton Impact Excitation (2s - 2p) with Li Atom
[12]
BAI Li-Hua;ZHANG Jing-Tao;ZHANG Qing-Gang;XU Zhi-Zhan. Time-Dependent Quantum Dynamics of T+CH4 → CH3 +HT Reaction
[13]
DUAN Xu-Ru;H. Lange;QIAN Shang-Jie;N. Lang. Density Distributions of H and H2 in Pulsed Microwave Hydrogen Plasmas
[14]
FU Rongtang;YU Zhigang;HUANG Qingfeng;SUN Xin;FU Rouli*. Dynamical Process of Charge Transfer in Fullerene C60
2017, Vol. 34 
