Sun Shichao, Yong Haiwang, Chen Feng, Mukamel Shaul
Department of Chemistry and Department of Physics & Astronomy, University of California Irvine USA
Chem Sci. 2022 Aug 11;13(35):10327-10335. doi: 10.1039/d2sc02768b. eCollection 2022 Sep 14.
The coherent ring current of Mg-phthalocyanine created by a broad band UV-visible pump pulse shows variation with time, where the ring currents at the corner benzene rings, around the Mg cation and on the outer ring oscillate with different time periods and the current density migrates among these regions. The 7 pairs of degenerate excited states populated upon photoexcitation, generate 21 distinct coherent ring currents. We further calculate the time-resolved X-ray circular dichroism (TRXCD) spectrum of the coherences contributing to the ring current obtained by an attosecond X-ray probe pulse resonant with the nitrogen K-edge. A frequency domain TRXCD signal obtained by a Fourier transform of the signal with respect to the pump-probe delay time clearly separates the currents induced by different state pairs.
由宽带紫外可见泵浦脉冲产生的镁酞菁的相干环电流随时间变化,其中角苯环、镁阳离子周围和外环处的环电流以不同的时间周期振荡,并且电流密度在这些区域之间迁移。光激发时填充的7对简并激发态产生21种不同的相干环电流。我们进一步计算了由与氮K边共振的阿秒X射线探测脉冲获得的、对环电流有贡献的相干性的时间分辨X射线圆二色性(TRXCD)光谱。通过对信号相对于泵浦-探测延迟时间进行傅里叶变换得到的频域TRXCD信号清晰地分离了由不同状态对诱导的电流。