Challenges in XUV Photochemistry Simulations: A Case Study on Ultrafast Fragmentation Dynamics of the Benzene Radical Cation

被引:11
|
作者
Bazzi, Sophia [1 ,2 ]
Welsch, Ralph [1 ]
Vendrell, Oriol [1 ,3 ,4 ]
Santra, Robin [1 ,2 ,4 ,5 ]
机构
[1] DESY, Ctr Free Electron Laser Sci, Notkestr 85, D-22607 Hamburg, Germany
[2] Univ Hamburg, Dept Chem, Grindelallee 117, D-20146 Hamburg, Germany
[3] Aarhus Univ, Dept Phys & Astron, Ny Munkegade 120, DK-8000 Aarhus C, Denmark
[4] Hamburg Ctr Ultrafast Imaging, Luruper Chausee 149, D-22761 Hamburg, Germany
[5] Univ Hamburg, Dept Phys, Jungiusstr 9, D-20355 Hamburg, Germany
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2018年 / 122卷 / 04期
关键词
POLYCYCLIC AROMATIC-HYDROCARBONS; DENSITY-FUNCTIONAL THEORY; 2ND-ORDER PERTURBATION-THEORY; APPROXIMATE COUPLED-CLUSTER; EXCITED-STATE; NONADIABATIC RELAXATION; POLARIZATION PROPAGATOR; INTERSTELLAR CHEMISTRY; EXCITATION ENERGIES; MOLECULAR-DYNAMICS;
D O I
10.1021/acs.jpca.7b11543
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The challenges of simulating extreme ultraviolet (XUV)-induced dissociation dynamics of organic molecules on a multitude of coupled potential energy surfaces are discussed for the prototypical photoionization of benzene. The prospects of Koopmans' theorem-based electronic structure calculations in combination with classical trajectories and Tully's fewest switches surface hopping are explored. It is found that a Koopmans' theorem-based approach overestimates the CH dissociation barrier and thus underestimates the fragmentation yield. However, the nonadiabatic population dynamics are in good agreement with previous approaches, indicating that the Koopmans' theorem based potentials are well described around the Franck-Condon point. This is explicitly tested for the ground state potential of the benzene cation employing CASPT2 calculations, for which very good agreement is found. This work highlights the need for efficient electronic structure approaches that can treat medium-sized organic molecules with a multitude of coupled excited states and several dissociation channels.
引用
收藏
页码:1004 / 1010
页数:7
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