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首页> 外文期刊>The Journal of Chemical Physics >Mixed semiclassical initial value representation time-averaging propagator for spectroscopic calculations
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Mixed semiclassical initial value representation time-averaging propagator for spectroscopic calculations

机译:混合半经典初始值表示时间平均传播子,用于光谱计算

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A mixed semiclassical initial value representation expression for spectroscopic calculations is derived. The formulation takes advantage of the time-averaging filtering and the hierarchical properties of different trajectory based propagation methods. A separable approximation is then introduced that greatly reduces (about an order of magnitude) the computational cost compared with a full Herman-Kluk time-averaging semiclassical calculation for the same systems. The expression is exact for the harmonic case and it is tested numerically for a Morse potential coupled to one or two additional harmonic degrees of freedom. Results are compared to full Herman-Kluk time-averaging calculations and exact quantum wavepacket propagations. We found the peak positions of the mixed semiclassical approximations to be always in very good agreement with full quantum calculations, while overtone peak intensities are lower with respect to the exact ones. Given the reduced computational effort required by this new mixed semiclassical approximation, we believe the present method to make spectroscopic calculations available for higher dimensional systems than accessible before. (C) 2016 AIP Publishing LLC.
机译:导出了用于光谱计算的混合半经典初始值表示表达式。该公式利用了时间平均滤波和基于不同轨迹的传播方法的分层特性。然后引入了一个可分离的近似值,与相同系统的完整Herman-Kluk时间平均半经典计算相比,它大大降低了(大约一个数量级)计算成本。该表达式对于谐波情况是准确的,并且对与一个或两个附加谐波自由度耦合的莫尔斯电势进行了数值测试。将结果与完整的Herman-Kluk时间平均计算和精确的量子波包传播进行比较。我们发现混合半经典近似值的峰位置始终与完整的量子计算非常吻合,而泛音峰强度相对于精确峰强度较低。鉴于这种新的混合半经典近似方法所需的计算量减少了,我们相信本方法可以使光谱计算可用于比以前更易使用的高维系统。 (C)2016 AIP出版有限责任公司。

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