当前位置：
X-MOL 学术
›
J. Phys. Chem. Lett.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
E to Z Photoisomerization of Phytochrome Cph1Δ Exceeds the Born–Oppenheimer Adiabatic Limit
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2019-06-10 00:00:00 , DOI: 10.1021/acs.jpclett.9b01137 Laurie A. Bizimana 1 , Camille A. Farfan 1 , Johanna Brazard 1 , Daniel B. Turner 1
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2019-06-10 00:00:00 , DOI: 10.1021/acs.jpclett.9b01137 Laurie A. Bizimana 1 , Camille A. Farfan 1 , Johanna Brazard 1 , Daniel B. Turner 1
Affiliation
|
The Born–Oppenheimer adiabatic limit applies broadly in chemistry because most reactions occur on the ground electronic state. Photochemical reactions involve two or more electronic states and need not be subject to this adiabatic limit. The spectroscopic signatures of nonadiabatic processes are subtle, and therefore, experimental investigations have been limited to the few systems dominated by single photochemical outcomes. Systems with branched excited-state pathways have been neglected, despite their potential to reveal insights into photochemical reactivity. Here we present experimental evidence from coherent three-dimensional electronic spectroscopy that the E to Z photoisomerization of phytochrome Cph1 is strongly nonadiabatic, and the simulations reproduce the measured features only when the photoisomerization proceeds nonadiabatically near, but not through, a conical intersection. The results broaden the general understanding of photoisomerization mechanisms and motivate future studies of nonadiabatic processes with multiple outcomes arising from branching on excited-state potential energy surfaces.
中文翻译：
植物色素Cph1Δ的E到Z光异构化超过了Born–Oppenheimer绝热极限
玻恩-奥本海默绝热极限在化学中广泛应用，因为大多数反应都发生在基态电子状态。光化学反应涉及两个或多个电子状态，并且不需要遵守该绝热极限。非绝热过程的光谱特征是微妙的，因此，实验研究仅限于以单一光化学结果为主导的少数系统。尽管具有揭示光化学反应性的潜能，但具有分支激发态途径的系统已被忽略。在这里，我们从相干三维电子光谱学中获得实验证据，即E到Z植物色素Cph1的光致异构化是高度绝热的，并且仅当光致异构化非绝热地在圆锥形交叉点附近而不是通过圆锥形交叉点进行时，模拟才重现测量的特征。结果拓宽了对光异构化机理的一般理解，并激发了非绝热过程的未来研究，其在激发态势能面上的分支产生了多种结果。
更新日期：2019-06-10
中文翻译：
植物色素Cph1Δ的E到Z光异构化超过了Born–Oppenheimer绝热极限
玻恩-奥本海默绝热极限在化学中广泛应用，因为大多数反应都发生在基态电子状态。光化学反应涉及两个或多个电子状态，并且不需要遵守该绝热极限。非绝热过程的光谱特征是微妙的，因此，实验研究仅限于以单一光化学结果为主导的少数系统。尽管具有揭示光化学反应性的潜能，但具有分支激发态途径的系统已被忽略。在这里，我们从相干三维电子光谱学中获得实验证据，即E到Z植物色素Cph1的光致异构化是高度绝热的，并且仅当光致异构化非绝热地在圆锥形交叉点附近而不是通过圆锥形交叉点进行时，模拟才重现测量的特征。结果拓宽了对光异构化机理的一般理解，并激发了非绝热过程的未来研究，其在激发态势能面上的分支产生了多种结果。
京公网安备 11010802027423号