A Photochemical Reaction in Different Theoretical Representations.
A Photochemical Reaction in Different Theoretical Representations.
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DOI：
10.1021/acs.jpca.1c09604
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发表时间：
2022-02-24
期刊：
影响因子：
--
通讯作者：
Agostini F
中科院分区：
文献类型：
--
作者：
Ibele LM;Curchod BFE;Agostini F
玻恩-奥本海默的照片塑造了我们对光化学过程的表现和解释，从光激发到通过一个锥形的交叉点，一个连接不同电子状态的漏斗。在这项工作中，我们分析了一个完整的硅光化学实验，从激光脉冲的显式电子激发到通过锥形相交的非辐射衰变后光产物的形成，通过对比玻恩-奥本海默提供的图像和精确分解提出的图像。精确分解提供了对光化学的另一种理解，它不依赖于诸如电子态、非绝热耦合和锥形相交等概念。在对两态二维模型系统进行非绝热量子动力学的基础上，这项工作使我们能够比较Born-Oppenheimer和精确分解(i)具有和不具有Condon近似的显式光激发，（ii）核波包通过圆锥形交叉点，（iii） frank - Condon区域中激发态的形成，（iv）在精确分解图像中使用经典和量子轨迹来捕获由激光脉冲触发的非绝热过程。
The Born–Oppenheimer picture has forged our representation and interpretation of photochemical processes, from photoexcitation down to the passage through a conical intersection, a funnel connecting different electronic states. In this work, we analyze a full in silico photochemical experiment, from the explicit electronic excitation by a laser pulse to the formation of photoproducts following a nonradiative decay through a conical intersection, by contrasting the picture offered by Born–Oppenheimer and that proposed by the exact factorization. The exact factorization offers an alternative understanding of photochemistry that does not rely on concepts such as electronic states, nonadiabatic couplings, and conical intersections. On the basis of nonadiabatic quantum dynamics performed for a two-state 2D model system, this work allows us to compare Born–Oppenheimer and exact factorization for (i) an explicit photoexcitation with and without the Condon approximation, (ii) the passage of a nuclear wavepacket through a conical intersection, (iii) the formation of excited stationary states in the Franck–Condon region, and (iv) the use of classical and quantum trajectories in the exact factorization picture to capture nonadiabatic processes triggered by a laser pulse.
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影响因子：
4.4
作者：
Abedi, Ali;Maitra, Neepa T.;Gross, E. K. U.
通讯作者：
Gross, E. K. U.
影响因子：
4.1
作者：
FEIT, MD;FLECK, JA;STEIGER, A
通讯作者：
STEIGER, A
影响因子：
8.6
作者：
Abedi, Ali;Maitra, Neepa T.;Gross, E. K. U.
通讯作者：
Gross, E. K. U.
影响因子：
1.6
作者：
Agostini, Federica;Tavernelli, Ivano;Ciccotti, Giovanni
通讯作者：
Ciccotti, Giovanni
影响因子：
4.4
作者：
Agostini, Federica;Abedi, Ali;Gross, E. K. U.
通讯作者：
Gross, E. K. U.