Fully anharmonic IR and Raman spectra of medium-size molecular systems: accuracy and interpretation.
Fully anharmonic IR and Raman spectra of medium-size molecular systems: accuracy and interpretation.
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DOI：
10.1039/c3cp53413h
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发表时间：
2014-02-07
期刊：
影响因子：
--
通讯作者：
Bloino J
中科院分区：
文献类型：
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作者：
Barone V;Biczysko M;Bloino J
在谐波近似下计算中、大分子体系的全红外（IR）和拉曼光谱（包括绝对强度和跃迁能）是当代计算化学最有趣的挑战之一。与普遍的看法相反，低阶微扰理论能够提供高精度的结果（实际上往往比从目前的直接动力学方法发出的结果更好），只要非谐共振得到适当的管理。这种观点概述了我们的研究小组最近的发展，发展了一个强大的和用户友好的虚拟光谱仪，植根于二阶振动微扰理论（VPT 2），也可由非专业人员基本上作为一个黑盒程序。几个例子明确制定，以说明我们的计算工具的功能，连同最重要的正在进行的发展。
Computation of full infrared (IR) and Raman spectra (including absolute intensities and transition energies) for medium- and large-sized molecular systems beyond the harmonic approximation is one of the most interesting challenges of contemporary computational chemistry. Contrary to common beliefs, low-order perturbation theory is able to deliver results of high accuracy (actually often better than those issuing from current direct dynamics approaches) provided that anharmonic resonances are properly managed. This perspective sketches the recent developments in our research group toward the development a robust and user-friendly virtual spectrometer rooted into the second-order vibrational perturbation theory (VPT2) and usable also by non-specialists essentially as a black-box procedure. Several examples are explicitly worked out in order to illustrate the features of our computational tool together with the most important ongoing developments.