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Xt Section the Various Operational Definitions of As Prototypes for the Structural Units T)R Poly,1Tnrni!: Lljole­ Distmlc(', and [Ingles Are Gin'n

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Xt Section the Various Operational Definitions of As Prototypes for the Structural Units T)R Poly,1Tnrni!: Lljole­ Distmlc(', and [Ingles Are Gin'n Molecular structures of gas-phase polyatomic molecules determined by spectroscopic methods Cite as: Journal of Physical and Chemical Reference Data 8, 619 (1979); https://doi.org/10.1063/1.555605 Published Online: 15 October 2009 Marlin D. Harmony, Victor W. Laurie, Robert L. Kuczkowski, R. H. Schwendeman, D. A. Ramsay, Frank J. Lovas, Walter J. Lafferty, and Arthur G. Maki ARTICLES YOU MAY BE INTERESTED IN A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu The Journal of Chemical Physics 132, 154104 (2010); https://doi.org/10.1063/1.3382344 Determination of Molecular Structure from Microwave Spectroscopic Data American Journal of Physics 21, 17 (1953); https://doi.org/10.1119/1.1933338 Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen The Journal of Chemical Physics 90, 1007 (1989); https://doi.org/10.1063/1.456153 Journal of Physical and Chemical Reference Data 8, 619 (1979); https://doi.org/10.1063/1.555605 8, 619 © 1979 American Institute of Physics for the National Institute of Standards and Technology. Molecular Structures of Gas-Phase Polyatomic Molecules Determined by Spectroscopic Methods Marlin D. Harmony Department of Cherni..str)', The University of Kansas, Lawrence, KS 66045 Victor W. Laurie Department of Chemistry, Princeton Unit'er.it)", Princeton, NJ 08540 Robert L. Kuczkowski Department of Chemistry, University of Michigan, Ann Arbor, Ml48109 R. H. Schwendeman Department of Chemistry, Michigan State University, East Lansing, MI 48824 D. A. Ramsay Her::;berg institute of Astrophysics, National Research COl/neil of Canada, OIlf1l<'U, KIA ORG, Canada Frank J. Lovas, Walter J. Lafferty, and Arthur G. Maki National Bureau of Standards, Washing/Oil, DC 20334 Spectroscopic data related to the structures of polyatomic molecules in the gas phase have been reviewed, critically evaluated, and compiled. All reported bond distances and angles have been classified as equilibrium (r 0)' average (r,), substitution (r.), or effective (ro) parameters, and have been given a quality rating which is a measure of the parameter uncertainty. The surveyed literature includes work from all of the areas of gas-phase spectroscopy from which precise quantitative struc· tural information can be derived. Introductory material includes definitions of the various types of parameters and a description of the evaluation procedure. Key words: Bond angles; bond distances; gas·phase polyatomic molecules; gas·phase spectroscopy; microwave spectroscopy; molecular conformation; molecular spectroscopy; molecular structure; molecules; SLrUClure. Contents Page Page 1. Introduction.... .. ............. 619 Inorganic Molecules ....................... 628 2. Definitions of Structural Parameters ......... 620 C1 Molecules ............................. 650 3. Uncertainties ............................ 623 C~ Molecules ............................. 668 4,. Evaluation Procedure ..................... 625 C3 Molecules ............................. 688 5. Description of Tables ..................... 625 c.! Molecules ............................. 702 Appendix: Selected Diatomic Molecule Distances .. 627 C5-C 11 Molecules .......................... 711 Structural Data Tables ....................... 628 1. Introduction distances and angJes and nuclear conformations-by analysis of molecular rotational constants. At the same time, precision uv-visible, infrared, and Haman spectro­ 31m:e tIll:: ftnl j'cpUrl~ uf high j'e~ululiun microwave scopy have yielded valuable structural results on relatively spectra more than thirty years ago, the microwave spectra small molecules, and more recently molecular beam of hundreds of molecules have heen examined. By far the reasommce methods have played a small but important most common aim of these studies has been the determina­ role. This report is a critical evaluation and compilation tion of geometrical structural parameters-internuclear of gas-phase structural data for polyatomic molecules determined by these techniques. The literature surveyed © 1979 by the U.S. Secretary of Commerce on behalf of the United States. This copyright is assigned to the American Institute in this work covers largely the time period from the late of Physics and the American Chemical. Society. 1940's through 1976 and approximately half-way into 1977. 0047-2689/79/030619-99/$06.50 619 J. Phys. Chern. Ref. Dalu, Vol. 8, No.3, 1979 620 HARMONY ET AL. TII(' ni t icaJ td~k tiC ~1I pphiJi~ ,1\(' f1CCC'l:'S,I1'V Liblir,graphic fullm,ing section. Unecrtainties i)l the reported parameters SllpP(lrt lJ:lc iJCl'lI performed by tite\alluLlul Bureau of have been reassessed by the revie,\'ers alld reported St[lll.!ank nlthOllgh the Londolt-niirnstein tables [1. 2]1 according \0 R conf;istent sclw,me. Fin'llly, when it rl"prearerl h:we ,dsu Lleen useful in .iocating pertinent literature. We to be necessary, distances and angles have been recalcu­ have trieJ. [,1 il~clLlde in this survey an polyatomic molecules bted from the reported rotational COl1~tallls or from the fOT which reliabJe structuraJ datil. arc available for the spectra. Because there are many possible slight variations grmll1d electronic Slate from spectroscopic studies. Omis­ in metbods of analysis, reported parameters werc replaced sions have surely occurred, but it is hoped that they have by recalculated ones only whell the two sets differed by been held to a minimum. amount~ ou tside the ·estimated ullcertainties. In the early stages of l~is project, it had been planned The format for the presentatioll o~ the strllctural data to il~chlde diatomic molecules as well as polyatomics. Sub­ hilS been chosen for clarity and simplicity. Distances have sequently, several factors led to t;1f. om!ssio:l of this p:'lase been reported in X. (100 pm) units with no more than of the evaluation. First, Lovas and Tiemann [3J ha'I'E~ re­ thrf(' decimal digits, This choice is a result of the facl that, cently publi~hed a critical review of thc spectfill data of exerpl for a rel:lliydy'small lIumber of polyatomic mole­ all those diatomic molecules studied by microwave tech­ cllks, ('xperimfnlal and mGdel errors lead to phy;:icall.y niques up to 197-1. Seeomlly, Herzberg and Huber [fl·J mt'aJ1il1~less Ilumbers beyond 0.001 .t For angles, reporter! have near completion 11 comprehensive review of diatomic ill degrecs. only one dec:mal digit has been listed. Paramo molecules which will up-Io-date the spectral and molecubr ('1('1' IIllcerlainlies have been indieated by a letter rating properties presented in Ibe earlier tables of Herzberg [S J. (lI, B ... ) which defines a range of ullcertainty. This Since diatomic molecules are of funclamental importalJce ,"cheme was chosen not only for simplicity and clarity, but a::; lht:: l:ol"nerslUnc of slruclural elielIli::;lry, lilld O[tell also 10 discourage users from placing an unrealistic provide an important point of comparison for pol ya tmn ic fmphasis llpon minor variat'ions in parameters, or an undue molecules, a selection of diatomic distances has J)(~ell j 11- rdiaJJce upon ,a precise lIncertainty. As described below, eluded in an Append:x to this work. In order' :i:al nearly l11c lIl:eertainties ill struclural parameters for the all microwave structures might bc available in a 5iJl~k majority of polyatomic molecules are dominated by rota­ SO:lrce, the A?pendix includes 2.11 those molecll !es reviewed tion-vibration interaction:; which can be estimated only by Lovas and Tiemann [3]. Other molecules helVe hrcll within certain narrow ranges. selected for inclusion primarily on the basis of llteir role III the next section the various operational definitions of as prototypes for the structural units t)r polY,1tnrni!: llJole­ distmlc(', and [Ingles are gin'n. Following this, the method cules. of assessing ullcertltinties is described, and a discussion of 1 Previous comp: lations containi:1g gas-phase ~t rll(:t :11'<11 t 1(' general evaluation prf)cedures is presented. As a fmal data of polyatomic molecules include the tables by :;iullon prologue, a brief description i~ given of the format, COIl tent, [6:, Appendix VIII of Gord,\ and Cook [7J, 31:d Appcl\(:ix ~llld organizalion of the tabulnted data. VI of Heno:berg [8J. The most recent compilation is tklt of Callomol1 <?t al, C2] covering 6.ts-pha3e sp,'clrosc<>pic 2. DeflnitiDn5 Df Structural Paramefers and diffraction data. For diatomic molecules, in addition to the sources mentioned in the previous paragraph, Tile' Hamiltonian used to <lnalyze the rot!.<tional spectra struclural data have been compiled ;l)' Hosen [9J anJ. have of mn" I mnleellles COl1si£ts of "ome collection of the also appeared III the .IAl\iAl< Thermochemical Tables [10 J. f(lllo .... in'" trrms: The primary aim of the presenl ,\-ork is the critical evaluation and compilation of reliable structural data (1) according to a set of relatively well-defined guidelines. The ::lCn + 3en + ;:ICQ + 3CI + JCm evaluation procedure is described in more detail in subse­ quent sections, but in general it results in Ihe inclusion of ill whic:h :il'n is Ilw rigid rotator Hamiltonian, :JCD is the o:d)' those stn:ctural results that are reliauly determined by cOJltributiOl: I'rnrn c'~IJ\ri:llgal distortion, :-rCQ describes the experimental data and are free of assumptions, intuition, Iluclrar quadrupole interaction, 3e] contains the internal and analogy, For the most part, this means t"nat only those rotalioc] ellel'g;y, and ;ILlll
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