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In search of the next Holy Grail of polyoxide chemistry: Explicitly correlated ab initio full quartic force fields for HOOH, HOOOH, HOOOOH, and their isotopologues
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10.1063/1.3684231
/content/aip/journal/jcp/136/8/10.1063/1.3684231
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/8/10.1063/1.3684231

Figures

Image of FIG. 1.
FIG. 1.

The CCSD(T)-F12/cc-pVQZ-F12 optimized equilibrium geometry of HOOH. To the precision given, this is also the CCSD(T)-F12/cc-pVTZ-F12 geometry, with the exception of the OO bond length, which is 1.451 Å at this level of theory.

Image of FIG. 2.
FIG. 2.

The CCSD(T)-F12/cc-pVTZ-F12 geometry of trans-HOOOH, the isomer for which experimental results are available. The structure has C 2 symmetry, and only unique geometric features are labeled.

Image of FIG. 3.
FIG. 3.

CCSD(T)-F12/cc-pVTZ-F12 geometry for chain isomer 1, predicted to be the lowest energy chain structure of HO4H. This structure has C 1 symmetry, and thus all geometric parameters are shown. The inset shows the view looking down the O2–O3 bond, useful for distinguishing the structures qualitatively.

Image of FIG. 4.
FIG. 4.

CCSD(T)-F12/cc-pVTZ-F12 geometry for chain isomer 2, predicted to lie 0.63 kcal mol−1 above chain 1. This structure has C 2 symmetry, and thus only unique geometric parameters are shown. The inset shows the view looking down the O2–O3 bond, useful for distinguishing the structures qualitatively.

Image of FIG. 5.
FIG. 5.

CCSD(T)-F12/cc-pVTZ-F12 geometry for chain isomer 3, predicted to lie 0.87 kcal mol−1 above chain 1. This structure has C 2 symmetry, and thus only unique geometric parameters are shown. The inset shows the view looking down the O2–O3 bond, useful for distinguishing the structures qualitatively.

Image of FIG. 6.
FIG. 6.

The three chain isomers, viewed with the O2–O3 bond perpendicular to the plane of the paper. Isomer 3 is portrayed in its stereoisomeric form.

Image of FIG. 7.
FIG. 7.

Newman-like projections of the three HO4H chain isomers.

Tables

Generic image for table
Table I.

Spectroscopic features at the CCSD(T)-F12 level of theory with various basis sets for HOOH, DOOD, and compared with experiment. All values are in cm−1. Note that VnZ refers to the cc-pVnZ-F12 basis sets, as discussed in the text. Experimental values are from gas phase spectra unless otherwise indicated. Values for other possible isotopologues with H, D, 16O, 17O, and 18O are included in the supplementary material (Ref. 78).

Generic image for table
Table II.

Experimental and theoretical rotational constants, in MHz, for HOOH at the CCSD(T)-F12/cc-pVnZ-F12 level of theory with zero-point and centrifugal distortion corrections included. The cc-pVnZ-F12 basis sets are represented in the table as simply VnZ.

Generic image for table
Table III.

Experimental and theoretical rotational constants, in MHz, for HOOOH and DOOOD at the CCSD(T)-F12/cc-pVnZ-F12 level of theory with zero-point and centrifugal distortion corrections included. The cc-pVnZ-F12 basis sets are represented in the table as simply VnZ.

Generic image for table
Table IV.

Spectroscopic features for HOOOH, DOOOD, DOOOH, and predicted at the CCSD(T)-F12/cc-pVTZ-F12 level of theory. All values are in cm−1. Note that the experimental results were obtained in argon matrices. Values for all other possible isotopologues with H, D, 16O, 17O, and 18O are included in the supplementary material (Ref. 78).

Generic image for table
Table V.

CCSD(T)-F12/cc-pVTZ-F12 fundamental vibrational frequencies for the HO4H and DO4D isotopologues of chain isomers 1, 2, and 3. All values are given in cm−1. (No irreducible representations are given for 1 since it has C 1 symmetry.) The modes are ν1, O4 torsion; ν2 and ν3, HO3 torsions; ν4 to ν8, various OOO bends and OO stretches; ν9 and ν10, HOO bends; ν11 and ν12, OH stretches. Values for all other possible isotopologues with H, D, 16O, 17O, and 18O are included in the supplementary material (Ref. 78).a

Generic image for table
Table VI.

Computed rotational constants, in MHz, for HO4H and DO4D isotopologues of all three chain isomers at the CCSD(T)-F12/cc-pVTZ-F12 level of theory with zero-point and centrifugal distortion corrections included. More isotopologues, as well as values computed with the cc-pVDZ-F12 basis set, are included in the supplementary information (Ref. 78).

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/content/aip/journal/jcp/136/8/10.1063/1.3684231
2012-02-24
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: In search of the next Holy Grail of polyoxide chemistry: Explicitly correlated ab initio full quartic force fields for HOOH, HOOOH, HOOOOH, and their isotopologues
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/8/10.1063/1.3684231
10.1063/1.3684231
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