Gas-phase NMR spectra demonstrating the effect of weak intermolecular forces on the NMR shielding constants of the interacting species are reported. We analyse the interaction of the molecular hydrogen isotopomers with He, Ne, and Ar, and the interaction in the He-CO_2 dimer. The same effects are studied for all these systems in the ab initio calculations. The comparison of the experimental and computed shielding constants is shown to depend strongly on the treatment of the bulk susceptibility effects, which determine in practice the pressure dependence of the experimental values. Best agreement of the results is obtained when the bulk susceptibility correction in rare gas solvents is evaluated from the analysis of the He-rare gas interactions, and when the shielding of deuterium in D_2-rare gas systems is considered.
Robust nuclear hyperpolarization of small molecules through intermolecular transfer of parahydrogen-derived polarization
NVision Imaging Technologies GmbH（NVision成像技术有限公司）；Institute of Chemical Physics, Vilnius University（维尔纽斯大学化学物理研究所）；Institut für Theoretische Physik, Universität Ulm（乌尔姆大学理论物理研究所）；Center for Integrated Quantum Science and Technology (IQST)（集成量子科学与技术中心）；Dipartimento di Medicina, Scienze della Vita e dell’Ambiente, Università degli studi dell’Aquila（阿奎拉大学生命与环境科学医学系）；Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne（洛桑联邦理工学院化学科学与工程研究所）
Measurements of Diffusion Coefficients of CO$_{2}$ in 1-Butanol with a New Laminar Jet Apparatus and PFG-NMR, Pointing to Interfacial Mass Transfer Effects
Investigation of real-fluid effects on NH$_3$ oxidation and blending characteristics at supercritical conditions via high-order Virial equation of state coupled with ab initio intermolecular potentials
Revving up 13C NMR shielding predictions across chemical space: Benchmarks for atoms-in-molecules kernel machine learning with new data for 134 kilo molecules
Ionization-Driven Dehydrogenation and Molecular Growth in Gas-Phase Adamantane Clusters
Université Caen Normandie, ENSICAEN, CNRS, CEA, Normandie Univ, CIMAP UMR6252（卡昂诺曼底大学，ENSICAEN，法国国家科学研究中心，法国原子能和替代能源委员会）；Lund University（隆德大学）；University of Gothenburg（哥德堡大学）；Institute of Physical Chemistry, Polish Academy of Sciences（波兰科学院物理化学研究所）
Unveiling the photophysics of thiourea from CASPT2/CASSCF potential energy surfaces and singlet/triplet excited state molecular dynamics simulations
本文从激发态和基态势能面的形貌和混合单重态/三重态量子经典分子动力学模拟推断的信息出发，描述了光激发硫脲在气相和溶液中的衰变机制。我们的气相结果揭示了T1/S 0系间交叉作为占主导地位的（49%）的内在衰变通道的基态，达到人口0.28在我们的模拟的最后时间（10 ps）。T1的布居将发生在从光谱S2电子态到S1的内部转换之后，随后是S1->T2系间穿越和T2->T1内部转换过程。还观察到仅沿单重态歧管发生的次要衰变通道，即S2-> S 0（33%）和S1-> S 0（18%），在气相中光激发硫脲的弛豫中起作用。在我们的模拟中明确纳入水-硫脲相互作用被发现挑起一个非常显着的延迟衰减到系统的基态，没有过渡到S 0被注册在我们的模拟的第一个10 ps。分子间的振动能量重新分配和明确的氢键之间建立的相互作用和硫脲的NH 2基团被发现在结构上或能量上阻碍访问的系统间的交叉或内部转换漏斗与基态。
