Editorial of the PCCP themed issue "Spectroscopy and dynamics of medium-sized molecules and clusters".
Editorial of the PCCP themed issue "Spectroscopy and dynamics of medium-sized molecules and clusters".
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PCCP主题期刊“中型分子和团簇的光谱学和动力学”的编辑。
DOI：
10.1039/c3cp90047a
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
M. Hochlaf
中科院分区：
文献类型：
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作者：
M. Hochlaf
“中等大小分子和团簇的光谱学和动力学”主题问题旨在介绍最先进的实验和理论光谱学和量子动力学。其中一个主要的课题是处理中等大小的分子和团簇在基态或激发态的非谐性。贡献概述，例如，高激发态的分子（包括电子，振动和旋转激发），弱约束聚集系统，动态的分子经历构象变化，动态的分子吸附在纳米结构，分子在低温下，分子在不寻常的环境（如，星际空间），大气分子和远距离粒子传输的准确描述。本期文章涵盖微波、远红外、红外、紫外-可见光和XUV能量领域。相关的光谱，以及它们的特异性和挑战都很好地显示出来。理论著作还揭示了用于这些目的的最先进的方法，其有效性以及如何超越常见和标准的近似值。具体而言，Csaszar等人的论文。(DOI：10.1039/C3 CP 44610 G），Tyuterev等人(DOI：10.1039/C3 CP 50275 A），Nikitin等人(DOI：10.1039/C3 CP 50799 H），Christiansen等人(DOI：10.1039/C3 CP 50283 J）和Tennyson等人。(DOI：10.1039/C3 CP 50303 H）以及赫尔曼和佩里的观点文章（DOI：10.1039/C3 CP 50463 H）报道了从头算和有效的基于哈密顿的方法，用于产生小分子的旋转振动态和旋转振动光谱。（如H3+、SO 3、CH 4/CD 4）和更大的体系（如吡啶和吡啶与银阳离子之间的络合物）。的理论预测与可用的实验光谱（带的位置和强度）的密切协议是惊人的，这验证了所提出的技术。这些作者指出，这种良好的一致性取决于多维势能面（PES）纳入他们的核运动处理计算的准确性。Hochlaf及其同事的论文（DOI：10.1039/C3 CP 44429 E和DOI：10.1039/C3 CP 44708 A）和Rauhut等人的论文。(DOI：10.1039/C3 CP 50172 H）开发用于产生大气重要电荷转移四原子复合物的全维PES的新策略，用于散射计算和聚类以及如何模拟势能面展开中的高阶项。在电子计算中，显关联（R）CCSD（T）-F12方法被认为能正确描述排斥壁、货车德瓦耳斯极小值和大的核间距。扩散基组是强制性的，以正确地考虑长程相互作用。对基准系统进行了处理，
The ‘‘Spectroscopy and dynamics of medium-sized molecules and clusters’’themed issue is aimed to present stateof-the art experimental and theoretical spectroscopy and quantum dynamics. One of the principal topics is the treatment of anharmonicity in medium-sized molecules and clusters either in their ground or excited electronic states. The contributions overview, for instance, accurate descriptions of highly excited states of molecules (including electronic, vibrational and rotational excitation), weakly bound aggregated systems, dynamics of molecules undergoing conformational changes, dynamics of molecules adsorbed on nanostructures, molecules at cold temperatures, molecules in unusual environments (eg, interstellar space), atmospheric molecules and long range particle transfers. The articles of this issue cover the microwave, far infra-red, infra-red, UV-Vis and XUV energy domains. The associated spectroscopies, and their specificities and challenges are nicely shown. The theoretical works also reveal the state-of-the-art methodologies used for these purposes, their validity and how to go beyond the common and standard approximations. Specifically, the papers by Csaszar et al.(DOI: 10.1039/C3CP44610G), Tyuterev et al.(DOI: 10.1039/C3CP50275A), Nikitin et al.(DOI: 10.1039/C3CP50799H), Christiansen et al.(DOI: 10.1039/C3CP50283J) and Tennyson et al.(DOI: 10.1039/C3CP50303H) and the perspective article by Herman and Perry (DOI: 10.1039/C3CP50463H) report ab initio and effective Hamiltonian-based approaches for the generation of the rotational–vibrational states and the rovibrational spectra of small (such as H3+, SO3, CH4/CD4) and larger systems (such as pyridine and the complex between pyridine and a silver cation). The close agreement of the theoretical predictions with the available experimental spectra (for both band positions and intensities) is striking, which validates the proposed techniques. These authors point out that such good agreement depends on the accuracy of the multidimensional potential energy surfaces (PESs) incorporated into their nuclear motion treatment calculations. The papers by Hochlaf and co-workers (DOI: 10.1039/C3CP44429E and DOI: 10.1039/C3CP44708A) and by Rauhut et al.(DOI: 10.1039/C3CP50172H) develop new strategies for the generation of full dimensional PESs for atmospherically important charge transfer tetratomic complexes, for scattering calculations and clustering and how to model the high-order terms in the potential energy surface expansions. For electronic computations, the explicitly correlated (R) CCSD (T)-F12 method is considered to correctly describe the repulsive wall, the van der Waals minimum and the large internuclear distances. A diffuse basis set is mandatory to correctly account for long range interactions. Benchmark systems are treated,