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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Local-mode approach to modeling multidimensional infrared spectra of metal carbonyls
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Local-mode approach to modeling multidimensional infrared spectra of metal carbonyls

机译：局部模式模拟金属羰基金属的多维红外光谱

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摘要

We present a general approach for modeling multidimensional infrared spectra based on a combination of phenomenological fitting and ab initio electronic structure calculations. The vibrational Hamiltonian is written in terms of bilinearly coupled Morse oscillators that represent local carbonyl stretches. This should be contrasted with the previous approach, where the anharmonic Hamiltonian was given in terms of normal-mode coordinates (Baiz et al.J. Phys. Chem. A 2009, 113, 9617). The bilinearly coupled Morse oscillator Hamiltonian is parametrized such that the frequencies and couplings are consistent with experiment, and the anharmonicities are computed by density functional theory. The advantages of the local-mode versus normal-mode approaches are discussed, as well as the ability of different density functionals to provide accurate estimates of the model parameters. The applicability and usefulness of the new approach are demonstrated in the context of the recently measured multidimensional infrared spectra of dimanganese decacarbonyl. The shifts in local site frequencies, couplings, and anharmonicities due to hydrogen bonding to the individual carbonyls are explored. It is found that, even though the effect of hydrogen bonding is nonlocal, it is additive.
机译：我们提出了一种基于现象学拟合和从头算电子结构计算的组合来建模多维红外光谱的通用方法。振动哈密顿量用表示局部羰基拉伸的双线性耦合摩尔斯振荡器写成。这应该与之前的方法形成对比，在以前的方法中，非谐哈密顿量是根据法向模坐标给出的（Baiz等人，J。Phys。Chem。A 2009，113，9617）。对双线性耦合的摩尔斯振荡器哈密顿量进行参数化，使其频率和耦合与实验一致，并通过密度泛函理论计算非谐性。讨论了本地模式与普通模式方法的优点，以及不同密度功能提供模型参数准确估计的能力。在最近测得的十羰基二锰多维红外光谱的背景下，证明了该新方法的适用性和实用性。探究了由于氢键合到各个羰基上引起的局部位点频率，耦合和非谐性的变化。已经发现，即使氢键的作用不是局部的，它也是加和的。

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