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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Effect of nuclear motion on molecular high order harmonic pump probe spectroscopy
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Effect of nuclear motion on molecular high order harmonic pump probe spectroscopy

机译:核运动对分子高阶谐波泵浦探针光谱的影响

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We study pump-probe schemes for the real time observation of electronic motion on attosecond time scale in the molecular ion H2~+ and its heavier isotope T2~+ while these molecules dissociate on femtosecond time scale by solving numerically the non-Born-Oppenheimer time-dependent Schr?dinger equation. The UV pump laser pulse prepares a coherent superposition of the three lowest lying quantum states and the time-delayed mid-infrared, intense few-femtosecond probe pulse subsequently generates molecular high-order harmonics (MHOHG) from this coherent electron-nuclear wavepacket (CENWP). Varying the pump-probe time delay by a few hundreds of attoseconds, the MHOHG signal intensity is shown to vary by orders of magnitude. Due to nuclear movement, the coherence of these two upper states and the ground state is lost after a few femtoseconds and the MHOHG intensity variations as function of pump-probe delay time are shown to be equal to the period of electron oscillation in the coherent superposition of the two upper dissociative quantum states. Although this electron oscillation period and hence the periodicity of the harmonic spectra are quite constant over a wide range of internuclear distances, a strong signature of nuclear motion is seen in the actual shapes and ways in which these spectra change as a function of pump-probe delay time, which is illustrated by comparison of the MHOHG spectra generated by the two isotopes H2~+ and T2~+. Two different regimes corresponding roughly to internuclear distances R < 4a_0 and R > 4a_0 are identified: For R < 4a_0, the intensity of a whole range of frequencies in the plateau region is decreased by orders of magnitude when the delay time is changed by a few hundred attoseconds whereas in the cutoff region the peaks in the MHOHG spectra are red-shifted with increasing pump-probe time delay. For R > 4a_0, on the other hand, the peaks both in the cutoff and plateau region are red-shifted with increasing delay times with only slight variations in the peak intensities. A time-frequency analysis shows that in the case of a two-cycle probe pulse the sole contribution of one long and associated short trajectory correlates with the attenuation of a whole range of frequencies in the plateau region for R < 4a_0 whereas the observed red shift for R > 4a_0, even in the plateau region, correlates with a single electron return within one-half laser cycle.
机译:我们研究了在分子离子H2〜+及其重同位素T2〜+中在亚秒级时域上实时观察电子运动的泵浦探针方案,同时通过数值求解非伯恩-奥本海默时间,这些分子在飞秒时标上解离相关的薛定ding方程。紫外泵浦激光脉冲准备了三个最低量子态的相干叠加,延时的中红外,强几个飞秒的探测脉冲随后从该相干电子核波包(CENWP)生成分子高阶谐波(MHOHG) )。将泵浦探测时间延迟改变几百个阿秒,MHOHG信号强度显示出数量级的变化。由于核运动,这两个较高状态和基态的相干性在几飞秒后消失,并且作为泵浦探针延迟时间函数的MHOHG强度变化与相干叠加中的电子振荡周期相等两个上解离量子态中的一个尽管该电子振荡周期以及因此谐波谱的周期性在很宽的核间距离范围内都是相当恒定的,但在实际形状和方式中这些谱随泵浦探针的变化而变化的核运动是很明显的延迟时间,通过比较两个同位素H2〜+和T2〜+生成的MHOHG光谱来说明。确定了两个大致对应于核间距离R <4a_0和R> 4a_0的不同状态:对于R <4a_0,当延迟时间改变几倍时,高原区域中整个频率范围的强度降低了几个数量级。百Attoseconds,而在截止区域中,MHOHG光谱中的峰随着泵浦探测时间延迟的增加而红移。另一方面,对于R> 4a_0,截止时间和平稳区域的峰都随着延迟时间的增加而红移,并且峰强度只有很小的变化。时频分析表明,在两周期探测脉冲的情况下,一个长且相关的短轨迹的唯一贡献与高原区域中R <4a_0的整个频率范围的衰减相关,而观察到的红移对于R> 4a_0,即使在高原区域,也与半个激光周期内的单个电子返回相关。

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