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Network-Based Design of Near-Infrared Lamb-Dip Experiments and the Determination of Pure Rotational Energies of H218O at kHz Accuracy 基于网络的近红外Lamb-Dip实验设计及H218O在kHz精度下的纯旋转能测定
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-06-15 DOI: 10.1063/5.0052744
M. Diouf, Roland Tóbiás, Irén Simkó, F. Cozijn, E. Salumbides, W. Ubachs, A. Császár
Taking advantage of the extreme absolute accuracy, sensitivity, and resolution of noise-immune-cavity-enhanced optical-heterodyne-molecular spectroscopy (NICE-OHMS), a variant of frequency-comb-assisted Lamb-dip saturation-spectroscopy techniques, the rotational quantum-level structure of both nuclear-spin isomers of H218O is established with an average accuracy of 2.5 kHz. Altogether, 195 carefully selected rovibrational transitions are probed. The ultrahigh sensitivity of NICE-OHMS permits the observation of lines with room-temperature absorption intensities as low as 10−27 cm molecule−1, while the superb resolution enables the detection of a doublet with a separation of only 286(17) kHz. While the NICE-OHMS experiments are performed in the near-infrared window of 7000–7350 cm−1, the lines observed allow the determination of all the pure rotational energies of H218O corresponding to J values up to 8, where J is the total rotational quantum number. Both network and quantum theory have been employed to facilitate the measurement campaign and the full exploitation of the lines resolved. For example, to minimize the experimental effort, the transitions targeted for observation were selected via the spectroscopic-network-assisted precision spectroscopy (SNAPS) scheme built upon the extended Ritz principle, the theory of spectroscopic networks, and an underlying dataset of quantum chemical origin. To ensure the overall connection of the ultraprecise rovibrational lines for both nuclear-spin isomers of H218O, the NICE-OHMS transitions are augmented with six accurate microwave lines taken from the literature. To produce absolute ortho-H218O energies, the lowest ortho energy is determined to be 23.754 904 61(19) cm−1. A reference, benchmark-quality line list of 1546 transitions, deduced from the ultrahigh-accuracy energy values determined in this study, provides calibration standards for future high-resolution spectroscopic experiments between 0–1250 and 5900–8380 cm−1.
利用频率梳辅助Lamb-dip饱和光谱技术的一种变体——抗噪声腔增强光外差分子光谱技术(nices - ohms)极高的绝对精度、灵敏度和分辨率,建立了H218O两种核自旋异构体的旋转量子级结构,平均精度为2.5 kHz。总共研究了195个精心挑选的旋转振动跃迁。NICE-OHMS的超高灵敏度允许观察到室温吸收强度低至10−27 cm分子−1的谱线,而极好的分辨率可以检测到分离率仅为286(17)kHz的双重态。而NICE-OHMS实验是在7000-7350 cm−1的近红外窗口中进行的,观察到的谱线允许确定H218O的所有纯旋转能,对应于J值高达8,其中J为总旋转量子数。网络和量子理论都被用来促进测量活动和充分利用已解决的线路。例如,为了最大限度地减少实验工作量,通过基于扩展里兹原理、光谱网络理论和量子化学起源基础数据集的光谱网络辅助精密光谱(SNAPS)方案选择观测目标跃迁。为了确保H218O的两种核自旋异构体的超精密振动线的整体连接,NICE-OHMS跃迁增加了来自文献的6条精确微波线。为了得到h218o的绝对邻位能,确定了最低邻位能为23.754 904 61(19)cm−1。根据本研究确定的超高精度能量值推导出1546个跃迁的参考基准质量线清单,为未来0-1250和5900-8380 cm−1之间的高分辨率光谱实验提供了校准标准。
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引用次数: 6
Speed-of-Sound Measurements and a Fundamental Equation of State for Propylene Glycol 丙二醇的声速测量和基本状态方程
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-06-01 DOI: 10.1063/5.0050021
T. Eisenbach, Christian W. Scholz, R. Span, Diego E. Cristancho, E. Lemmon, M. Thol
A fundamental equation of state was developed for propylene glycol. It is written in terms of the Helmholtz energy with the independent variables temperature and density. Due to its fundamental nature, it can be used to calculate all thermodynamic state properties from the Helmholtz energy and its derivatives with respect to the independent variables. Special attention was paid not only to accurately reproduce the available experimental data but also to correct extrapolation. Therefore, this equation can be used for application in mixture models. For the development of the present equation of state, the available literature data were supplemented with new experimental speed-of-sound measurements, which were conducted in the temperature range from 293.2 K to 353.2 K with pressures up to 20 MPa. High accuracy was achieved by applying the well-established double-path-length pulse-echo technique and a careful sample preparation.
建立了丙二醇的基本状态方程。它是用亥姆霍兹能和温度和密度作为自变量来表示的。由于它的基本性质,它可以用来计算所有热力学状态的性质,从亥姆霍兹能量和它对自变量的导数。特别注意的是,不仅要准确地再现现有的实验数据,而且要正确地外推。因此,该方程可用于混合模型。在293.2 ~ 353.2 K的温度范围内,在20 MPa的压力下,对已有的文献数据进行了补充。通过应用成熟的双路长度脉冲回波技术和精心的样品制备,获得了高精度。
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引用次数: 5
Recommended Correlations for the Surface Tension of n-Alkanes 正构烷烃表面张力的推荐相关性
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-05-14 DOI: 10.1063/5.0048675
Á. Mulero, I. Cachadiña, D. Bautista
In previous papers, specific correlations were proposed to reproduce the surface tension values selected for several families of fluids and for wide ranges of temperatures. In this paper, the surface tension of n-alkanes is considered. For that, the data available in DIPPR and DETHERM databases and in Wohlfarth and Wohlfarth [“Surface tension of pure liquids and binary liquid mixtures,” in Landolt-Bornstein, New Series Group IV Physical Chemistry Vol. 16, edited by M. D. Lechner (Springer-Verlag, Berlin, 1997)] and its updated supplements (2008 and 2016) have been compiled. In most cases, a significant number of new data have been added, which were published elsewhere during the last few years and that were not included in the previously mentioned sources. All the data and values available for each fluid have been carefully screened and subsequently fitted to the Guggenheim–Katayama model, which includes two to six adjustable coefficients for each fluid. As a result, recommended correlations for 33 n-alkanes are proposed, providing absolute deviations below 1.65 mN/m and mean absolute percentage deviations below 2.1%.
在以前的论文中,提出了特定的相关性来重现为几个流体家族和宽温度范围选择的表面张力值。本文考虑了正构烷烃的表面张力。为此,DIPPR和DETHERM数据库以及Wohlfarth和Wohlfarth[“纯液体和二元液体混合物的表面张力”,Landolt Bornstein,New Series Group IV Physical Chemistry Vol.16,由M.D.Lechner编辑(Springer Verlag,Berlin,1997)]及其更新的补充资料(2008年和2016年)中的可用数据已经汇编完毕。在大多数情况下,增加了大量新数据,这些数据在过去几年中在其他地方发布,但没有包括在前面提到的来源中。每种流体的所有可用数据和值都经过了仔细筛选,随后拟合到古根海姆-片山模型中,该模型包括每种流体两到六个可调节系数。因此,提出了33种正构烷烃的推荐相关性,其绝对偏差低于1.65 mN/m,平均绝对百分比偏差低于2.1%。
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引用次数: 8
Cross Sections for Electron Collisions with H2O 电子与H2O碰撞的截面
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-05-12 DOI: 10.1063/5.0035315
Mi-Young Song, Hyuck Cho, G. Karwasz, V. Kokoouline, Yoshiharu Nakamura, J. Tennyson, A. Faure, N. Mason, Y. Itikawa
Electron collision cross section data for the water molecule are compiled from the literature. Cross sections are collected and reviewed for total scattering, elastic scattering, momentum transfer, excitations of rotational and vibrational states, electronic excitation, dissociation, ionization, and dissociative attachment. For each of these processes, the recommended values of the cross sections are presented. The literature has been surveyed up to the end of 2019.
根据文献汇编了水分子的电子碰撞截面数据。收集并回顾了总散射、弹性散射、动量转移、旋转和振动态激发、电子激发、解离、电离和解离附着的截面。对于这些过程中的每一个,都给出了截面的推荐值。文献调查截止到2019年底。
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引用次数: 14
Positron Scattering from the Group IIB Metals Zinc and Cadmium: Recommended Cross Sections and Transport Simulations IIB族金属锌和镉的正电子散射:推荐截面和输运模拟
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-05-04 DOI: 10.1063/5.0046091
P. Stokes, R. White, R. McEachran, F. Blanco, G. García, M. Brunger
Results from the application of our optical potential and relativistic optical potential models to positron scattering from gas-phase zinc (Zn) and cadmium (Cd) are presented. In particular, integral cross sections (ICSs) for elastic scattering, positronium formation, summed discrete electronic-state excitation, and ionization scattering processes are reported for both species and over an extended incident positron energy range. From those ICSs, the total cross section is subsequently constructed by taking their sum. We note that there are currently no experimental data available for any of these scattering processes for either species, with earlier computational results being limited to the elastic channel and restricted to relatively narrow incident positron energy regimes. Nonetheless, we construct recommended positron cross section datasets for both zinc and cadmium over the incident positron energy range of 0–10 000 eV. The recommended positron cross section data are subsequently employed in a multi-term Boltzmann equation analysis to simulate the transport of positrons, under the influence of an applied (external) electric field, through the background Zn and Cd gases. Qualitatively similar behavior in the calculated transport coefficients was observed between both species. Finally, for the case of zinc, the present positron transport coefficients are compared against corresponding results from electron transport with some significant differences now being observed.
介绍了我们的光学势和相对论光学势模型在气相锌和镉正电子散射中的应用结果。特别是,在扩展的入射正电子能量范围内,报道了弹性散射、正电子形成、加和离散电子态激发和电离散射过程的积分截面(ICSs)。根据这些ICSs,随后通过取其总和来构造总横截面。我们注意到,目前还没有任何实验数据可用于这两种物质的任何散射过程,早期的计算结果仅限于弹性通道,并且仅限于相对较窄的入射正电子能量范围。尽管如此,我们构建了锌和镉在0–10入射正电子能量范围内的推荐正电子截面数据集 000eV。推荐的正电子截面数据随后被用于多项玻尔兹曼方程分析,以模拟正电子在外加(外部)电场的影响下通过背景Zn和Cd气体的传输。在计算的传输系数中,在两个物种之间观察到了定性相似的行为。最后,对于锌的情况,将目前的正电子输运系数与电子输运的相应结果进行了比较,目前正在观察到一些显著的差异。
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引用次数: 2
Rate Constants for Abstraction of H from the Fluoromethanes by H, O, F, and OH H、O、F和OH从氟甲烷中提取H的速率常数
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-04-14 DOI: 10.1063/5.0028874
Donald R Burgess, J. A. Manion
In this work, we compiled and critically evaluated rate constants from the literature for abstraction of H from the homologous series consisting of the fluoromethanes (CH3F, CH2F2, and CHF3) and methane (CH4) by the radicals H atom, O atom, OH, and F atom. These reactions have the form RH + X → R + HX. Rate expressions for these reactions are provided over a wide range of temperatures (300–1800 K). Expanded uncertainty factors f (2σ) are provided at both low and high temperatures. We attempted to provide rate constants that were self-consistent within the series—evaluating the system, not just individual reactions. For many of the reactions, the rate constants in the literature are available only over a limited temperature range (or there are no reliable measurements). In these cases, we predicted the rate constants in a self-consistent manner employing relative rates for other reactions in the homologous series using empirical structure–activity relationships, used empirical correlations between rate constants at room temperature and activation energies at high temperatures, and used relative rates derived from ab initio quantum chemical calculations to assist in rate constant predictions.
在这项工作中,我们从文献中编译并严格评估了由H原子、O原子、OH原子和F原子组成的由氟甲烷(CH3F、CH2F2和CHF3)和甲烷(CH4)组成的同源系列中提取H的速率常数。这些反应的形式是RH + X→R + HX。在较宽的温度范围内(300 - 1800k)给出了这些反应的速率表达式。在低温和高温下均给出了扩展不确定因子f (2σ)。我们试图提供在系列中自洽的速率常数-评估系统,而不仅仅是单个反应。对于许多反应,文献中的速率常数仅在有限的温度范围内可用(或者没有可靠的测量)。在这些情况下,我们利用经验构效关系,以自一致的方式预测了同源系列中其他反应的相对速率,利用室温下的速率常数与高温下的活化能之间的经验相关性,并利用从头算量子化学计算得出的相对速率来辅助速率常数的预测。
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引用次数: 4
New Equations of State for Binary Hydrogen Mixtures Containing Methane, Nitrogen, Carbon Monoxide, and Carbon Dioxide 含甲烷、氮、一氧化碳和二氧化碳的二元氢混合物的新状态方程
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-03-01 DOI: 10.1063/5.0040533
R. Beckmüller, M. Thol, I. Bell, E. Lemmon, R. Span
New equations of state for the binary mixtures H2 + CH4, H2 + N2, H2 + CO2, and H2 + CO are presented. The results are part of an ongoing research project aiming at an improvement of the GERG-2008 model for the description of hydrogen-rich multicomponent mixtures. The equations are formulated in terms of the reduced Helmholtz energy and allow for the calculation of all thermodynamic properties over the entire fluid surface including the gas phase, liquid phase, supercritical region, and equilibrium states. The mathematical structure of the new mixture models corresponds to the form chosen for the reference model GERG-2008 of Kunz and Wagner [J. Chem. Eng. Data 57, 3032 (2012)]. In this way, the equations can be implemented into the existing framework of the GERG-2008 model. The ranges of validity of the new equations correspond to the normal and extended ranges of validity of the GERG-2008 model.
提出了新的二元混合物H2 + CH4、H2 + N2、H2 + CO2和H2 + CO的状态方程。这些结果是一个正在进行的研究项目的一部分,该项目旨在改进描述富氢多组分混合物的geg -2008模型。这些方程是用简化亥姆霍兹能量来表示的,可以计算整个流体表面的所有热力学性质,包括气相、液相、超临界区域和平衡状态。新混合模型的数学结构与Kunz和Wagner的参考模型geg -2008所选择的形式相对应[J]。化学。Eng。数据57,3032(2012)]。这样,方程就可以被实现到现有的geg -2008模型框架中。新方程的效度范围对应于geg -2008模型的正常效度范围和扩展效度范围。
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引用次数: 15
Recommended Cross Sections for Electron–Indium Scattering 电子-铟散射的推荐截面
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-01-29 DOI: 10.1063/5.0035218
K. Hamilton, O. Zatsarinny, K. Bartschat, M. Rabasovic, D. Šević, B. Marinković, S. Dujko, J. Atić, D. Fursa, I. Bray, R. McEachran, F. Blanco, G. García, P. Stokes, R. White, D. B. Jones, L. Campbell, M. Brunger
We report, over an extended energy range, recommended angle-integrated cross sections for elastic scattering, discrete inelastic scattering processes, and the total ionization cross section for electron scattering from atomic indium. In addition, from those angle-integrated cross sections, a grand total cross section is subsequently derived. To construct those recommended cross-section databases, results from original B-spline R-matrix, relativistic convergent close-coupling, and relativistic optical-potential computations are also presented here. Electron transport coefficients are subsequently calculated, using our recommended database, for reduced electric fields ranging from 0.01 Td to 10 000 Td using a multiterm solution of Boltzmann’s equation. To facilitate those simulations, a recommended elastic momentum transfer cross-section set is also constructed and presented here.
我们报道了在扩展的能量范围内,弹性散射、离散非弹性散射过程的推荐角度积分截面,以及原子铟电子散射的总电离截面。此外,从这些角度积分的横截面,随后导出了一个大的总横截面。为了构建这些推荐的截面数据库,本文还介绍了原始B样条R矩阵、相对论收敛紧耦合和相对论光学势计算的结果。随后,使用我们推荐的数据库计算了0.01 Td至10范围内的减小电场的电子输运系数 000Td,使用Boltzmann方程的长期解。为了便于这些模拟,本文还构建并提出了一个推荐的弹性动量传递截面集。
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引用次数: 4
Fifty Years of the Journal of Physical and Chemical Reference Data 《物理与化学杂志》参考资料50年
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-01-25 DOI: 10.1063/5.0038318
D. Lide
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引用次数: 15
Fifty Years of Reference Data 五十年参考数据
IF 4.3 2区 工程技术 Q1 Physics and Astronomy Pub Date : 2021-01-25 DOI: 10.1063/5.0040316
A. Harvey, Donald R. Burgess
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引用次数: 1
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Journal of Physical and Chemical Reference Data
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