Ultrafast imaging of laser-controlled non-adiabatic dynamics in NO2 from time-resolved photoelectron emission

被引:9
作者
Richter, Maria [1 ,2 ]
Gonzalez-Vazquez, Jesus [1 ]
Masin, Zdenek [2 ,5 ]
Brambila, Danilo S. [2 ]
Harvey, Alex G. [2 ]
Morales, Felipe [2 ]
Martin, Fernando [1 ,3 ,4 ]
机构
[1] Univ Autonoma Madrid, Dept Quim, Modulo 13, E-28049 Madrid, Spain
[2] Max Born Inst, Max Born Str 2A, D-12489 Berlin, Germany
[3] Inst Madrileno Estudios Avanzados Nanociencia IMD, Madrid 28049, Spain
[4] Univ Autonoma Madrid, Condensed Matter Phys Ctr IFIMAC, E-28049 Madrid, Spain
[5] Charles Univ Prague, Fac Math & Phys, Inst Theoret Phys, V Holesovickach 2, Prague 18000 8, Czech Republic
关键词
POTENTIAL-ENERGY SURFACES; CONICAL INTERSECTION DYNAMICS; EXCITED-STATE DYNAMICS; AB-INITIO; VIBRATIONAL FREQUENCIES; ELECTRON LOCALIZATION; N(S-4)+O-2 REACTION; SYMMETRY-BREAKING; PROGRAM SYSTEM; LOWEST DOUBLET;
D O I
10.1039/c9cp00649d
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
Time-resolving and controlling coupled electronic and nuclear dynamics at conical intersections on the sub-femtosecond to few-femtosecond time scale is among the challenging goals of attosecond physics. Here we present numerical simulations of time-resolved photoelectron spectroscopy of such dynamics in NO2, where the coupled electron-nuclear motion at the (2)A(1)/B-2(2) conical intersection is steered on the sub-laser-cycle time scale by a nearly single-cycle, waveform controlled mid-infrared laser pulse. For a rigorous description of the photoionization dynamics, we employ ab initio energy-and geometryresolved photoionization matrix elements obtained with the multichannel R-matrix method, using a multiconfigurational description of the molecule and a newly developed algorithm to generate photoionization dipoles that are phase consistent on the level of both the neutral and the ionic states. We find that for sufficient molecular alignment, the time- and energy-resolved anisotropy parameters of the photoelectron angular distributions provide a particularly clear picture of both the ultrafast natural molecular dynamics at the conical intersection and its modifications by the control pulse. In particular, changes in the electronic and nuclear configurations induced by the control pulse lead to the appearance of non-vanishing odd anisotropy parameters in the photoelectron spectra. These are absent in the spectra obtained without the control pulse and therefore provide sensitive, background-free diagnostic of the control.
引用
收藏
页码:10038 / 10051
页数:14
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