Mixed Quantum-Classical Molecular Dynamics Analysis of the Molecular-Level Mechanisms of Vibrational Frequency Shifts
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- 作者：Christine M. Morales ; Ward H. Thompson
- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：June 28, 2007
- 年：2007
- 卷：111
- 期：25
- 页码：5422 - 5433
- 全文大小：539K
- 年卷期：v.111,no.25(June 28, 2007)
- ISSN：1520-5215
文摘
A detailed analysis of the origins of vibrational frequency shifts of diatomic molecules (I2 and ICl) in a raregas (Xe) liquid is presented. Specifically, vibrationally adiabatic mixed quantum-classical molecular dynamicssimulations are used to obtain the instantaneous frequency shifts and correlate the shifts to solventconfigurations. With this approach, important mechanistic questions are addressed, including the following:How many solvent atoms determine the frequency shift? What solvent atom configurations lead to blue shifts,and which lead to red shifts? What is the effect of solute asymmetry? The mechanistic analysis can be generallyapplied and should be useful in understanding what information is provided by infrared and Raman spectraabout the environment of the probed vibrational mode.