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UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans-Azobenzene
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-03-05 00:00:00 , DOI: 10.1021/acs.jpclett.8b00152 Artur Nenov 1 , Rocio Borrego-Varillas 2 , Aurelio Oriana 2 , Lucia Ganzer 2 , Francesco Segatta 1, 3 , Irene Conti 1 , Javier Segarra-Marti 4 , Junko Omachi 5 , Maurizio Dapor 3 , Simone Taioli 3, 6 , Cristian Manzoni 2 , Shaul Mukamel 7 , Giulio Cerullo 2 , Marco Garavelli 1
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-03-05 00:00:00 , DOI: 10.1021/acs.jpclett.8b00152 Artur Nenov 1 , Rocio Borrego-Varillas 2 , Aurelio Oriana 2 , Lucia Ganzer 2 , Francesco Segatta 1, 3 , Irene Conti 1 , Javier Segarra-Marti 4 , Junko Omachi 5 , Maurizio Dapor 3 , Simone Taioli 3, 6 , Cristian Manzoni 2 , Shaul Mukamel 7 , Giulio Cerullo 2 , Marco Garavelli 1
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We combine sub-20 fs transient absorption spectroscopy with state-of-the-art computations to study the ultrafast photoinduced dynamics of trans-azobenzene (AB). We are able to resolve the lifetime of the ππ* state, whose decay within ca. 50 fs is correlated to the buildup of the nπ* population and to the emergence of coherences in the dynamics, to date unobserved. Nonlinear spectroscopy simulations call for the CNN in-plane bendings as the active modes in the subps photoinduced coherent dynamics out of the ππ* state. Radiative to kinetic energy transfer into these modes drives the system to a high-energy planar nπ*/ground state conical intersection, inaccessible upon direct excitation of the nπ* state, that triggers an ultrafast (0.45 ps) nonproductive decay of the nπ* state and is thus responsible for the observed Kasha rule violation in UV excited trans-AB. On the other hand, cis-AB is built only after intramolecular vibrational energy redistribution and population of the NN torsional mode.
中文翻译：
紫外光诱导的振动相干性：理解反偶氮苯中违反Kasha规则的关键
我们将低于20 fs的瞬态吸收光谱技术与最新技术相结合，以研究反式超快光致动力学-偶氮苯（AB）。我们能够解析ππ*状态的寿命，该状态在ca内衰减。50 fs与nπ*种群的增加以及动力学中相干性的出现相关（迄今为止尚未发现）。非线性光谱模拟要求CNN平面内弯曲是子空间中ππ*状态以外的光子相干动力学中的激活模式。辐射到动能的辐射传递到这些模式，将系统驱动到高能平面nπ* /基态圆锥形交点，当直接激发nπ*状态时无法访问该圆锥形交点，从而触发nπ*状态的超快（0.45 ps）非生产性衰减因此造成了紫外线激发反光中观察到的Kasha规则违反-AB。另一方面，仅在分子内振动能重新分配并填充NN扭转模式后，才能建立cis-AB。
更新日期：2018-03-05
中文翻译：
紫外光诱导的振动相干性：理解反偶氮苯中违反Kasha规则的关键
我们将低于20 fs的瞬态吸收光谱技术与最新技术相结合，以研究反式超快光致动力学-偶氮苯（AB）。我们能够解析ππ*状态的寿命，该状态在ca内衰减。50 fs与nπ*种群的增加以及动力学中相干性的出现相关（迄今为止尚未发现）。非线性光谱模拟要求CNN平面内弯曲是子空间中ππ*状态以外的光子相干动力学中的激活模式。辐射到动能的辐射传递到这些模式，将系统驱动到高能平面nπ* /基态圆锥形交点，当直接激发nπ*状态时无法访问该圆锥形交点，从而触发nπ*状态的超快（0.45 ps）非生产性衰减因此造成了紫外线激发反光中观察到的Kasha规则违反-AB。另一方面，仅在分子内振动能重新分配并填充NN扭转模式后，才能建立cis-AB。
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