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Isomerization of nitrosomethane to formaldoxime: Energies, geometries, and frequencies from the parametric variational two-electron reduced-density-matrix method
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10.1063/1.3458641
/content/aip/journal/jcp/133/3/10.1063/1.3458641
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/3/10.1063/1.3458641

Figures

Image of FIG. 1.
FIG. 1.

Critical points on the potential energy surface for the isomerization of nitrosomethane to trans-formaldoxime as computed by the 2-RDM method in the aug-cc-pVTZ basis set. The dashed line represents a 1,3-hydrogen shift; the solid line represents successive 1,2-shifts. The figure shows that 1,2-shift is energetically more favorable than the 1,3-shift by about 10 kcal/mol.

Tables

Generic image for table
Table I.

Absolute energies of the stationary points on the potential energy surfaces corresponding to the rearrangement of nitrosomethane to formaldoxime via 1,3- or successive 1,2-hydrogen shifts. Results are given for the CCSD, CCSD(T), and 2-RDM methods in the aug-cc-pVTZ basis set. Zero-point vibrational energies as computed in the cc-pVDZ basis set are given in parentheses. All energies are reported in hartrees.

Generic image for table
Table II.

Relative energies of the stationary points on the potential energy surfaces corresponding to the rearrangement of nitrosomethane to formaldoxime via 1,3- or successive 1,2-hydrogen shifts. Results are given for the CCSD, CCSD(T), 2-RDM, and G2 methods in the aug-cc-pVTZ basis set and the MP2 method in the basis set. MP2 and G2 results are from Ref. 40. All energies are reported relative to the energy of nitrosomethane 1 in units of kcal/mol. The numbers that represent each stationary point correspond to those given in Fig. 1.

Generic image for table
Table III.

The energy of formaldonitrone relative to nitrosomethane in the cc-pVXZ basis sets, with , T, and Q and the CBS limit. In the CBS limit, both the 2-RDM and CCSD(T) methods predict that formaldonitrone is more stable than nitrosomethane, while CCSD predicts the opposite ordering. Energies are given in units of kcal/mol.

Generic image for table
Table IV.

Structural parameters for nitrosomethane, trans-formaldoxime, and formaldonitrone as computed by the CCSD, CCSD(T), and 2-RDM methods in the cc-pVDZ basis set. The subscripts i, o, c, and t denote in-plane, out-of-plane, cis-to-the-oxygen, and trans-to-the oxygen hydrogen atoms. Experimental values for nitrosomethane were obtained from Ref. 51. Experimental values for formaldoxime were taken from Refs. 52 and 53.

Generic image for table
Table V.

Harmonic frequencies for nitrosomethane, formaldonitrone, and the transition state for the cis-trans isomerization of formaldoxime 6 as computed by the CCSD, CCSD(T), and 2-RDM methods in the cc-pVDZ basis set. For each method the transition state 6 has only 11 frequencies with the final imaginary frequency omitted. All frequencies are given in .

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/content/aip/journal/jcp/133/3/10.1063/1.3458641
2010-07-20
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Isomerization of nitrosomethane to formaldoxime: Energies, geometries, and frequencies from the parametric variational two-electron reduced-density-matrix method
http://aip.metastore.ingenta.com/content/aip/journal/jcp/133/3/10.1063/1.3458641
10.1063/1.3458641
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