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141.
Takayoshi Ishimoto Masanori Tachikawa Umpei Nagashima 《International journal of quantum chemistry》2008,108(3):472-481
To optimize the exponent values in protonic and deuteronic Gaussian‐type functions (GTF) by the elimination of translational and rotational motions, we have proposed the new scheme of an analytical gradient formula with respect to the exponent values in the multi‐component molecular orbital scheme, which can take into account the quantum effects of protons and deuterons, under the Hartree‐Fock level of theory. Numerical assessment of H2 and D2 molecules confirms that there is a clear difference between distributions of protonic and deuteronic orbitals following the elimination of translational and rotational motions. In particular, the d‐type GTF in the protonic orbital drastically improves the total energy. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 相似文献
142.
Yang Zheng Dr. Junhua Chen Chunguo Duan Xinyue Zhang Dr. Xuefang Xu Dr. Qian Gou 《Chemphyschem》2023,24(7):e202200804
The pure rotational spectra of 1-phenylethanol and its monohydrate were measured by using a pulsed jet Fourier transform microwave spectrometer. One conformer of the 1-phenylethanol monomer with the trans form was observed in the pulsed jet. The experimental values of rotational constants of ten isotopologues, including eight mono-substituted 13C and one D isotopologues, allow an accurate structure determination of the skeleton of 1-phenylethanol. For its monohydrate, only one isomer has been observed, of which 1-phenylethanol adopts the trans form and binds with water through an O−H⋅⋅⋅Ow and an Ow−H⋅⋅⋅π hydrogen bond. Each rotational transition displays a doublet with a relative intensity ratio of 1 : 3, due to a hindered internal rotation of water around its C2 axis. This study provides the information on accurate geometry of 1-phenylethanol (PE) and large amplitude motion of water in the PE monohydrate. 相似文献
143.
Dr. Pablo Pinacho Dr. Donatella Loru Dr. Tatjana Šumanovac Dr. Marina Šekutor Prof. Dr. Melanie Schnell 《Chemphyschem》2023,24(23):e202300561
We report on the synthesis and characterization using high-resolution rotational spectroscopy of three bulky thioethers that feature an adamantyl group connected to a sulfur atom. Detailed experimental and theoretical structures are provided and compared with the 1,1′-diadamantyl ether. In addition, we expand on previous findings concerning microsolvation of adamantyl derivatives by investigating the cluster formation between these thioethers and a water molecule. The investigation of such clusters provides valuable insights into the sulfur-centered hydrogen bonding in thioethers with increasing size and steric repulsion. 相似文献
144.
Highly Unsaturated Platinum and Palladium Carbenes PtC3 and PdC3 Isolated and Characterized in the Gas Phase
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Dror M. Bittner Dr. Daniel P. Zaleski Dr. David P. Tew Dr. Nicholas R. Walker Prof.Dr. Anthony C. Legon 《Angewandte Chemie (International ed. in English)》2016,55(11):3768-3771
Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms. 相似文献
145.
Dr. Garrett K. Drayna Christian Hallas Kenneth Wang Dr. Sergio R. Domingos Sandra Eibenberger Prof. Dr. John M. Doyle David Patterson 《Angewandte Chemie (International ed. in English)》2016,55(16):4957-4961
Cooling molecules in the gas phase is important for precision spectroscopy, cold molecule physics, and physical chemistry. Measurements of conformational relaxation cross sections shed important light on potential energy surfaces and energy flow within a molecule. However, gas‐phase conformational cooling has not been previously observed directly. In this work, we directly observe conformational dynamics of 1,2‐propanediol in cold (6 K) collisions with atomic helium using microwave spectroscopy and buffer‐gas cooling. Precise knowledge and control of the collisional environment in the buffer‐gas allows us to measure the absolute collision cross‐section for conformational relaxation. Several conformers of 1,2‐propanediol are investigated and found to have relaxation cross‐sections with He ranging from σ=4.7(3.0)×10?18 cm2 to σ>5×10?16 cm2. Our method is applicable to a broad class of molecules and could be used to provide information about the potential energy surfaces of previously uninvestigated molecules. 相似文献
146.
Geometry of an Isolated Dimer of Imidazole Characterised by Rotational Spectroscopy and Ab Initio Calculations
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John C. Mullaney Dr. Daniel P. Zaleski Dr. David P. Tew Dr. Nicholas R. Walker Prof.Dr. Anthony C. Legon 《Chemphyschem》2016,17(8):1154-1158
An isolated, gas‐phase dimer of imidazole is generated through laser vaporisation of a solid rod containing a 1:1 mixture of imidazole and copper in the presence of an argon buffer gas undergoing supersonic expansion. The complex is characterised through broadband rotational spectroscopy and is shown to have a twisted, hydrogen‐bonded geometry. Calculations at the CCSD(T)(F12*)/cc‐pVDZ‐F12 level of theory confirm this to be the lowest‐energy conformer of the imidazole dimer. The distance between the respective centres of mass of the imidazole monomer subunits is determined to be 5.2751(1) Å, and the twist angle γ describing rotation of one monomer with respect to the other about a line connecting the centres of mass of the monomers is determined to be 87.9(4)°. Four out of six intermolecular parameters in the model geometry are precisely determined from the experimental rotational constants and are consistent with results calculated ab initio. 相似文献
147.
148.
传统的扭摆法测转动惯量多使用单线摆、三线摆等,针对传统的扭摆法测转动惯量装置的一些缺陷,比如由于产生摆动、计时方法不科学使计时结果不准确、装置不能保持在水平面上转动等造成的测量误差较大的问题,研究制造了一种新的实验装置。这套装置用涡卷弹簧提供扭摆的动力,用光电对管配合单片机进行精确计时,并且采用了变面接触为线接触等多种减小摩擦的设计来提高测量精度,使误差大大减小了。整套装置具有测量结果精确、操作简单、体积小、能测量不规则的及难以直立的物体的转动惯量、能很好地验证平行轴定理等优点。 相似文献
149.
Christian Renner Tad A. Holak 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2000,145(2):192
Based on the measurement of cross-correlation rates between 15N CSA and 15N–1H dipole–dipole relaxation we propose a procedure for separating exchange contributions to transverse relaxation rates (R2 = 1/T2) from effects caused by anisotropic rotational diffusion of the protein molecule. This approach determines the influence of anisotropy and chemical exchange processes independently and therefore circumvents difficulties associated with the currently standard use of T1/T2 ratios to determine the rotational diffusion tensor. We find from computer simulations that, in the presence of even small amounts of internal flexibility, fitting T1/T2 ratios tends to underestimate the anisotropy of overall tumbling. An additional problem exists when the N–H bond vector directions are not distributed homogeneously over the surface of a unit sphere, such as in helix bundles or β-sheets. Such a case was found in segment 4 of the gelation factor (ABP 120), an F-actin cross-linking protein, in which the diffusion tensor cannot be calculated from T1/T2 ratios. The 15N CSA tensor of the residues for this β-sheet protein was found to vary even within secondary structure elements. The use of a common value for the whole protein molecule therefore might be an oversimplification. Using our approach it is immediately apparent that no exchange broadening exists for segment 4 although strongly reduced T2 relaxation times for several residues could be mistaken as indications for exchange processes. 相似文献
150.
本文论述用角重迭方法计算配合物群重迭积分的一般形式,推导出在分子点群与旋转点群的群重迭积分之间存在简单关系,从而属于分子点群的群重迭积分可用属于旋转点群的群重迭积分表示,即群重迭积分可采用复函数形式计算.对角重迭模型计算的方法作了必要的简化。 相似文献