Interstellar silicon–nitrogen chemistry. III. The spectral signatures of the H2SiN+ molecular ion

Parisel, Olivier; Hanus, M.; Ellinger, Y.

doi:10.1063/1.470953

Cited by 16 publications

(8 citation statements)

References 46 publications

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“…the latter ionic species has so far been extensively investigated especially in relation to interstellar silicon-nitrogen chemistry. In particular, in order to understand the detection of the SiN radical in the interstellar medium, various experimental and theoretical studies [94][95][96][97][98] have been reported on singlet and triplet H-Si-N-H + , H 2 Si-N + and Si-NH 2 + isomeric structures. the singlet Si-NH 2 + resulted in by far the most stable isomer, separated by at least 215 kJ mol -1 from any other singlet or triplet isomeric structure.…”

Section: Reactions Of Nf Xmentioning

confidence: 99%

Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Antoniotti

Operti

Ragazzoni

et al. 2009

Eur J Mass Spectrom (Chichester)

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The positive ion chemistry occurring in silane/nitrogen trifluoride gaseous mixtures has been investigated by ion trap mass spectrometry. Reaction sequences and rate constants have been determined for the processes involving the primary ions SiH(n)(+) (n = 0-3) and NF(x)(+) (x = 1-3) and the secondary ions obtained from their reactions with SiH(4) and NF(3). The SiH(n)(+) efficiently react with NF(3) and undergo cascades of abstraction and scrambling reactions which form the fluorinated and perfluorinated cations SiHF(m)(+) (m = 1, 2), SiH(2)F(+) and SiF(x)(+) (x = 0-3). Fluorinated Si(2)- clusters such as Si(2)H(2)F(+), Si(2)H(3)F(+) and Si(2)H(5)F(+) were also observed. The reaction of both SiH(3)(+) and SiH(2)F(+) with NF(3) produces the elusive fluoronitrenium ion NHF(+). Any NF(x)(+) reacts with SiH(4) mainly by charge transfer. Additional ionic products are, however, observed which suggest intimate reaction complexes. Worth mentioning is the formation of SiNH(2)(+) from the reaction of both NF(+) and NHF(+) with SiH(4). The primary ions NF(2)(+) and SiH(2)(+) are also "sink" species in our observed chemistry.

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Section: Reactions Of Nf Xmentioning

confidence: 99%

Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Antoniotti

Operti

Ragazzoni

et al. 2009

Eur J Mass Spectrom (Chichester)

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“…As an example, scaled MPn, and even CCSD(T) approaches can lead to coherent IR spectra but the apparent convergence of the results may be biased by the fact that these methods all correspond to single-reference calculations: a correct treatment may request an accurate description of non-dynamic correlation effects [23] and thus the consideration of multireference methodologies. Such a failure of the MPn and CCSD(T) methods has been pointed out in the case of H2SiN ÷ [9] and will be unambiguously illustrated in the section devoted to HSiN.…”

Section: Scaling Procedures For the Rotational And Vibrational Constantsmentioning

confidence: 69%

“…It has however been recently pointed out that, when dealing with the C 9, C~t and C13 , entities the ordering of the harmonic frequencies and their intensities as well are crucially dependent on the size of the CASSCF space [23]. Within the present series of molecules, it can furthermore be noticed that single-reference approaches failed for HSiN and H2SiN + [9] that both contain Sill bonds, while succeeding in the description of both HNSi and SiNH~- [8] that do not. The spectacular changes observed in HSiN and H2SiN + when rising the calculation level up to CASSCF are however less pronounced for the HSiNH 2, H2SiNH and HSiNH + species that are considered in the next sections.…”

Section: Hsinmentioning

confidence: 71%

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Interstellar silicon-nitrogen chemistry. I. The microwave and the infrared signatures of the HSiN, HNSi, HSiNH2, HNSiH2 and HSiNH+ species

Parisel¹,

Hanus²,

Ellinger³

1996

Chemical Physics

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The experimental and the theoretical interests for the silicon chemistry have been renewed by the recent detection of SiN in space. In this contribution a theoretical study of the HSiN, HNSi, HSiNH 2 and HNSiH 2 molecular systems is presented that aims to help in the interpretation of available experimental results as well as in the attribution of new interstellar lines. The main goal of this report remains, however, the calibration of ab initio calculations on still-unknown silicon-nitrogen systems: the infrared and the microwave signatures of the HSiNH + cation are reported as a direct application. The signatures of the five molecules under investigation have been computed a t increasing levels of post-Hartree-Fock theories, using up to a 6-311 +-t-G * * atomic orbital expansion. Accurate geometries and B e rotational constants have been determined at the M~511er-Plesset MPn (n = 2, 3, 4), CASSCF and CCSD(T) theoretical plateaus for HNSi. The comparison with experimental data allows then to derive the scaling factors needed to obtain accurate rotational constants for related species: they are applied as such on the crude constants determined for HSiN, HSiNH 2, HNSiH 2, and finally HSiNH 2 in its floppy linear singlet ground state and in its lowest cis-bent a3p(state as well. Dipole moments are reported in order to assess the feasability for these species to be detected owing to their rotational signatures either in the laboratory or in space using millimetric radioastronomy techniques. Infrared (IR) signatures are computed at the same levels of theory and compared to the recent matrix isolation experiments devoted to HSiN, HNSi, HSiNH 2 and HNSiH 2. The calculations unambiguously confirm that all these species have been effectively produced and observed. They also lead to the determination of accurate IR scaling factors that are significantly larger than the usual ones. Such an approach allows then to quantitatively predict the IR spectra of the still-unknown HSiNH ÷ entity. The study of the IR spectra furthermore points out the failure of single-reference correlation methods to obtain predictive IR signatures in some cases, as is unambiguously illustrated in the case of the HSiN species.

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“…22 These identifications were supported by density functional theory and ab initio calculations. 18,20,21,[23][24][25][26][27] In the present study, we map the six-dimensional potential energy surfaces (6D-PESs) of the formaldehyde-like isomers (i.e., H 2 NSi and H 2 SiN) in their electronic ground state using the standard coupled cluster approach (RCCSD(T)/augcc-pV5Z) and using the newly implemented explicitly correlated RCCSD(T)-F12a/b techniques. This work does not treat the trans-HSiNH form because of the multiconfigurational nature of its wavefunction in contrast to the monoconfigurational nature of two others.…”

Section: Introductionmentioning

confidence: 99%

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

Lauvergnat

Senent

Jutier

et al. 2011

The Journal of Chemical Physics

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Various ab initio methods are used to compute the six dimensional potential energy surfaces (6D-PESs) of the ground states of the H(2)NSi and H(2)SiN radicals. They include standard coupled cluster (RCCSD(T)) techniques and the newly developed explicitly correlated RCCSD(T)-F12 methods. For H(2)NSi, the explicitly correlated techniques are viewed to provide data as accurate as the standard coupled cluster techniques, whereas small differences are noticed for H(2)SiN. These PESs are found to be very flat along the out-of-plane and some in-plane bending coordinates. Then, the analytic representations of these PESs are used to solve the nuclear motions by standard perturbation theory and variational calculations. For both isomers, a set of accurate spectroscopic parameters and the vibrational spectrum up to 4000 cm(-1) are predicted. In particular, the analysis of our results shows the occurrence of anharmonic resonances for H(2)SiN even at low energies.

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Interstellar silicon–nitrogen chemistry. III. The spectral signatures of the H2SiN+ molecular ion

Cited by 16 publications

References 46 publications

Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Interstellar silicon-nitrogen chemistry. I. The microwave and the infrared signatures of the HSiN, HNSi, HSiNH2, HNSiH2 and HSiNH+ species

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

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Interstellar silicon–nitrogen chemistry. III. The spectral signatures of the H2SiN+ molecular ion

Cited by 16 publications

References 46 publications

Positive Ion Chemistry of SiH4/NF3 Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Positive Ion Chemistry of SiH4/NF3 Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Interstellar silicon-nitrogen chemistry. I. The microwave and the infrared signatures of the HSiN, HNSi, HSiNH2, HNSiH2 and HSiNH+ species

Explicitly correlated treatment of H2NSi and H2SiN radicals: Electronic structure calculations and rovibrational spectra

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Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry

Positive Ion Chemistry of SiH₄/NF₃ Gaseous Mixtures Studied by Ion Trap Mass Spectrometry