Time-resolved spectra of I2 in a krypton crystal by G-MCTDH simulations: nonadiabatic dynamics, dissipation and environment driven decoherence.,Faraday Discussions

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Time-resolved spectra of I2 in a krypton crystal by G-MCTDH simulations: nonadiabatic dynamics, dissipation and environment driven decoherence.
Faraday Discussions ( IF 3.3 ) Pub Date : 2019-12-16 , DOI: 10.1039/c9fd00065h
David Picconi ₁ , Irene Burghardt

Affiliation

The multi-state photodynamics following the B 3Πu(0+) ← X 1Σ+g excitation of molecular iodine in a krypton crystal are studied quantum mechanically using the Gaussian variant of the multiconfigurational time-dependent Hartree method (G-MCTDH). Calculations are performed using a 9-state 18-dimensional Hamiltonian parametrized via diatomics-in-molecules calculations. The simulations reproduce the low predissociation yield deduced by time resolved spectroscopic experiments, and allow the elucidation of the diabatic population dynamics in the dense manifold of covalent electronic states of the embedded I2. The wave packet dynamics are used to calculate pump-probe spectra involving excited state absorption which terminates in the ion pair manifold. The simulated signals are in excellent agreement with the experimental ones, and are interpreted by reducing the full-dimensional wavefunction to the density matrix of the I2 subsystem. It is proved formally that the pump-probe traces can be obtained as convolution between the Wigner function of the chromophore and a time- and frequency-gate function also represented in the phase space. The analysis of the spectra with probe frequency in resonance with the β ← A 3Πu transition reveals that the mechanism of predissociation out of the B state is pump photon energy-dependent. The quantum nature of the nonradiative transitions is imprinted in the strongly non-classical features of the Wigner function on the A state surface, which is detected in the pump-probe process.

中文翻译：

通过G-MCTDH模拟得到a晶体中I2的时间分辨谱：非绝热动力学，耗散和环境驱动的退相干。

利用多构型时变哈特里方法（G-MCTDH）的高斯变体，对quantum晶体中分子碘的B3Πu（0+）←X1Σ+ g激发之后的多态光动力学进行了量子力学研究。通过分子中的双原子计算，使用9态18维哈密顿参数进行计算。该模拟重现了通过时间分辨光谱实验推导的低解离前产率，并且可以阐明嵌入的I2的共价电子态的密集流形中的非绝热种群动态。波包动力学用于计算涉及激发态吸收的泵浦探针光谱，该激发态吸收终止于离子对歧管中。模拟信号与实验信号非常吻合，和通过将全维波函数简化为I2子系统的密度矩阵来解释。正式证明，泵浦探针痕迹可以通过生色团的维格纳函数与相空间中也表示的时间和频率门函数之间的卷积获得。对探针频率与β←A3Πu跃迁共振的光谱的分析表明，从B态发生的预离解机理与泵浦光子能量有关。非辐射跃迁的量子性质被印在A态表面上Wigner函数的强烈非经典特征中，该特征在泵浦探测过程中被检测到。正式证明，泵浦探针痕迹可以通过生色团的维格纳函数与相空间中也表示的时间和频率门函数之间的卷积获得。对探针频率与β←A3Πu跃迁共振的光谱的分析表明，从B态发生的预离解机理与泵浦光子能量有关。非辐射跃迁的量子性质被印在A态表面上Wigner函数的强烈非经典特征中，该特征在泵浦探测过程中被检测到。正式证明，泵浦探针痕迹可以通过生色团的维格纳函数与相空间中也表示的时间和频率门函数之间的卷积获得。对探针频率与β←A3Πu跃迁共振的光谱的分析表明，从B态发生的预离解机理与泵浦光子能量有关。非辐射跃迁的量子性质被印在A态表面上Wigner函数的强烈非经典特征中，该特征在泵浦探测过程中被检测到。对探针频率与β←A3Πu跃迁共振的光谱的分析表明，从B态发生的预离解机理与泵浦光子能量有关。非辐射跃迁的量子性质被印在A态表面上Wigner函数的强烈非经典特征中，该特征在泵浦探测过程中被检测到。对探针频率与β←A3Πu跃迁共振的光谱的分析表明，从B态发生的预离解机理与泵浦光子能量有关。非辐射跃迁的量子性质被印在A态表面上Wigner函数的强烈非经典特征中，该特征在泵浦探测过程中被检测到。

更新日期：2020-01-13

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