Impact of Vibrational Coherence on the Quantum Yield at a Conical Intersection

详细信息    查看全文

• 作者：Hong-Guang Duan ; R. J. Dwayne Miller ; Michael Thorwart
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：September 1, 2016
• 年：2016
• 卷：7
• 期：17
• 页码：3491-3496
• 全文大小：369K
• 年卷期：0
• ISSN：1948-7185

文摘

We study the vibrationally coherent quantum dynamics of an electronic wave packet in the vicinity of a conical intersection within a three-state two-mode model. By transforming the coherent tuning and coupling modes into the bath, the underdamped dynamics of the resulting effective three-state model is solved efficiently by the numerically exact hierarchy equation of motion approach. The transient excited-state absorption and two-dimensional spectra reveal the impact of vibrational coherence on the relaxation pathways of the wave packet. We find that both the quantum yield and the isomerization rate are crucially influenced by the vibrational coherence of the wave packet. A less coherent wave packet can traverse the conical intersection more rapidly, while the resulting quantum yield is smaller. Finally, we show that repeated passages of the wave packet through the conical intersection can lead to measurable interference effects in the form of Stueckelberg oscillations.