MARVEL Analysis of the Measured High-Resolution Rovibronic Spectra and Definitive Ideal-Gas Thermochemistry of the 16O2 Molecule

IF 4.4 2区工程技术 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Physical and Chemical Reference Data Pub Date : 2019-04-10 DOI:10.1063/1.5083135

T. Furtenbacher, Mátyás Horváth, D. Koller, Panna Sólyom, Anna Balogh, I. Balogh, A. Császár

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引用次数: 17

Abstract

Accurate, empirical rovibronic energy levels, with associated uncertainties, are determined for the lowest seven electronic states of the 16O2 molecule using the MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm. After careful analysis and validation of 30 671 rovibronic transitions (including 24 376 measured and 6295 artificial transitions), collected from 91 publications, 4279 empirical rovibronic energy levels are determined. The highly accurate empirical (MARVEL) energy database is then augmented with rovibronic energies obtained from accurate effective Hamiltonians for the lowest six electronic states, establishing a hybrid database containing 15 946 rovibronic energy levels. Based on this hybrid database, complete up to the first dissociation limit, 41 260 cm−1, an accurate temperature-dependent ideal-gas partition function, Qint(T), and some related thermochemical functions [isobaric heat capacity, Cpo(T), entropy, So(T), and (absolute) enthalpy, Ho(T)] are derived for 16O2 employing the direct-summation technique. All thermochemical functions are reported, in 1 K increments up to 5000 K, in the supplementary material to this paper.Accurate, empirical rovibronic energy levels, with associated uncertainties, are determined for the lowest seven electronic states of the 16O2 molecule using the MARVEL (Measured Active Rotational-Vibrational Energy Levels) algorithm. After careful analysis and validation of 30 671 rovibronic transitions (including 24 376 measured and 6295 artificial transitions), collected from 91 publications, 4279 empirical rovibronic energy levels are determined. The highly accurate empirical (MARVEL) energy database is then augmented with rovibronic energies obtained from accurate effective Hamiltonians for the lowest six electronic states, establishing a hybrid database containing 15 946 rovibronic energy levels. Based on this hybrid database, complete up to the first dissociation limit, 41 260 cm−1, an accurate temperature-dependent ideal-gas partition function, Qint(T), and some related thermochemical functions [isobaric heat capacity, Cpo(T), entropy, So(T), and (absolute) enthalpy, Ho(T)] are derived for 16O2 em...

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16O2分子高分辨率振动光谱和理想气体热化学的漫威分析

使用MARVEL(实测主动旋转振动能级)算法，确定了16O2分子最低7个电子态的精确的、经验的振动能级和相关的不确定性。在仔细分析和验证了从91篇出版物中收集的30671个振动跃迁(包括24376个实测跃迁和6295个人工跃迁)后，确定了4279个经验振动能级。然后用最低6个电子态的精确有效哈密顿量得到的振动能级对高精度经验(MARVEL)能量数据库进行扩充，建立了包含15 946个振动能级的混合数据库。基于这一混合数据库，完成到第一个解离极限，41 260 cm−1，一个精确的温度依赖的理想气体配分函数，Qint(T)，和一些相关的热化学函数[等压热容，Cpo(T)，熵，So(T)，和(绝对)焓，Ho(T)]为16O2使用直接求和技术。在本文的补充材料中，报告了所有热化学函数，增量为1k至5000k。使用MARVEL(实测主动旋转振动能级)算法，确定了16O2分子最低7个电子态的精确的、经验的振动能级和相关的不确定性。在仔细分析和验证了从91篇出版物中收集的30671个振动跃迁(包括24376个实测跃迁和6295个人工跃迁)后，确定了4279个经验振动能级。然后用最低6个电子态的精确有效哈密顿量得到的振动能级对高精度经验(MARVEL)能量数据库进行扩充，建立了包含15 946个振动能级的混合数据库。基于这一混合数据库，完成到第一个解离极限，41 260 cm−1，一个精确的温度依赖的理想气体配分函数，Qint(T)，和一些相关的热化学函数[等压热容，Cpo(T)，熵，So(T)，和(绝对)焓，Ho(T)]，在16O2 em。

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来源期刊

Journal of Physical and Chemical Reference Data 化学-化学综合

CiteScore

6.90

自引率

11.60%

发文量

审稿时长

>12 weeks

期刊介绍： The Journal of Physical and Chemical Reference Data (JPCRD) is published by AIP Publishing for the U.S. Department of Commerce National Institute of Standards and Technology (NIST). The journal provides critically evaluated physical and chemical property data, fully documented as to the original sources and the criteria used for evaluation, preferably with uncertainty analysis. Critical reviews may also be included if they document a reference database, review the data situation in a field, review reference-quality measurement techniques, or review data evaluation methods.