Triplet methylnitrene: an indefinitely stable species in the absence of collisions

Demuynck, J.; Fox, Douglas J.; Yamaguchi, Yukio; Schaefer, Henry F.

doi:10.1021/ja00540a005

Cited by 56 publications

(27 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, the authors of this study suggested that lowering of the symmetry of the system and a more accurate account of the electronic correlation would lead to the disappearance of the barrier in accordance with the results of earlier calculations. 85,86 In 2000, a new attempt was made 93 to establish the presence of a barrier between the positions 1 [CH 3 N] and H 2 C = NH on the PES. The calculations were carried out by the CASSCF(12/11) and CASPT2 methods with the cc-pVDZ and cc-pVTZ basis sets.…”

Section: -Azidonorbornanementioning

confidence: 99%

Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

Gritsan¹

2007

Russ. Chem. Rev.

View full text Add to dashboard Cite

Section: -Azidonorbornanementioning

confidence: 99%

Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

Gritsan¹

2007

Russ. Chem. Rev.

View full text Add to dashboard Cite

“…There have been several computational studies of the dissociation of methyl azide, 15,18,[34][35][36] including the MNDO study by Bock and Dammel mentioned above. 31 Nguyen et al studied the potential energy surfaces at the UMP2 / 6-31G͑d , p͒ level of theory and computed the rate constants for the decomposition of methyl azide.…”

Section: Introductionmentioning

confidence: 99%

Understanding the rate of spin-forbidden thermolysis of HN3 and CH3N3

Besora

Harvey

2008

The Journal of Chemical Physics

View full text Add to dashboard Cite

The pyrolysis of the simplest azides HN(3) and CH(3)N(3) has been studied computationally. Nitrogen extrusion leads to the production of NH or CH(3)N. The azides have singlet ground states but the nitrenes CH(3)N and NH have triplet ground states. The competition between spin-allowed decomposition to the excited state singlet nitrenes and the spin-forbidden N(2) loss is explored using accurate electronic structure methods (CASSCF/cc-pVTZ and MR-AQCC/cc-pVTZ) as well as statistical rate theories. Nonadiabatic rate theories are used for the dissociation leading to the triplet nitrenes. For HN(3), (3)NH formation is predicted to dominate at low energy, and the calculated rate constant agrees very well with energy-resolved experimental measurements. Under thermal conditions, however, the singlet and triplet pathways are predicted to occur competitively, with the spin-allowed product increasingly favored at higher temperatures. For CH(3)N(3) thermolysis, spin-allowed dissociation to form (1)CH(3)N should largely dominate at all temperatures, with spin-forbidden formation of (3)CH(3)N almost negligible. Singlet methyl nitrene is very unstable and should rearrange to CH(2)NH immediately upon formation, and the latter species may lose H(2) competitively with vibrational cooling, depending on temperature and pressure.

show abstract

“…-2AK(;, + U(~2 -2/3) + Eaan + 1I2(E bb + Ecc)(2 _ ~2) + (A-B)K2+B[J(J+ 1) -2(K+~)~+2] -DKK4 -DNK [J(J + 1) -2(K + ~)~ + 2]K 2 -DN[(J(J+ 1)2-4~KJ(J+ 1) + (8-6~2)J(J+ 1) -(4 -6~2)K2 -2~K + 4(1 _ ~2)],where and (;, == «(; ILz + Gz 1(;)· Spin-uncoupling(JK,P + 1,~ + 1; ± IH IJKP~; ± ) = -[B-2DN[J(J+ 1) +K-1-2~] -DNKK2 -(Ebb + Ecc )/4] X [2J(J + 1) -2(K + ~)(K + ~ + 1)]112, (JK,P + 2,~ + 2; ± IH IJKP~; ± ) = -2D N [J(J+ 1) -K(K-1)]1I2[J(J+ 1) _ K(K + 1)] 1/2. Elements off-diagonal in K (J, -K + 2, -P+ 2, -~; ± IH'IJKP~; ±) ± (-I)J-K+ Ihl [J(J + 1) -(K + ~ -1)(K + ~ -2)]1/2[J(J + 1) -(K + ~)(K + ~ _1)]1/2, (J, -K + 2, -P+ 1, -~ -1; ± IH'IJKP~; ±) = ± (_l)J-K+ I(EI -2h l ) X [2J(J + 1) -2(K + ~)(K + ~ _1)]112, (J, -K + 2, -P, -~-2; ± IH'IJKP~; ±) = ±(_I)J-K+12(01+h l -E I ), (J, -K -1, -P-l, -~; ± IH'IJKP~; ±) = ± ( -I)J -K [h2 (2K + 1) + 2E2b~] X [J(J + 1) -(K + ~)(K + ~ + 1)]112, (J, -K -1, -P, -~ + 1; ± IH'IJKP~; ± ) ± ( -1)J-K [(E 2a -h2 )(2K + 1) + (02 -E 2b )(2~ -1)](2) 112.…”

mentioning

confidence: 99%

Rotational analysis of the 0 band of the Ã 3E–X̃ 3A2 system of methylnitrene

Brazier

Carrick

Bernath

1992

The Journal of Chemical Physics

View full text Add to dashboard Cite

Vibrational frequencies in the A3 E state of methylnitrene J. Chem. Phys. 94, 4678 (1991); 10.1063/1.460600Methylnitrene free radical. Ground state vibrational fundamentals and harmonic force field from jetcooled emission spectra of the A3 E-X3 A 2 band system J. Chem. Phys. 89, 6007 (1988); 10.1063/1.455415 Rotational analysis of the A←X̃ system of C2HThe optical emission spectrum of the methylnitrene radical has been observed at a resolution of 0.07 cm 1. Transitions to subbands with K up to 3 in the X 3 A z ground state were observed and a full rotational analysis carried out. Comparison of the structural information with the highest level theoretical calculations shows agreement to within the estimated error.

show abstract

Triplet methylnitrene: an indefinitely stable species in the absence of collisions

Cited by 56 publications

References 0 publications

Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

Study of photochemical transformations of organic azides by matrix isolation techniques and quantum chemistry

Understanding the rate of spin-forbidden thermolysis of HN3 and CH3N3

Rotational analysis of the 0 band of the Ã 3E–X̃ 3A2 system of methylnitrene

Contact Info

Product

Resources

About