Detection of Two Highly Stable Silicon Nitrides: HSiNSi and H<sub>3</sub>SiNSi

Crabtree, Kyle N.; Martı́nez, O.; McCarthy, Michael

doi:10.1021/jp4068119

Cited by 16 publications

(9 citation statements)

References 52 publications

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“…Support for this line of reasoning is provided by the recent detections of HSiNSi and H 3 SiNSi [55], HSiNH 2 [56], HCCNSi, and NCNSi [57] by this approach. Because the chemistry of SiN compounds is exceedingly rich [58], with many possible isomeric Downloaded by [New York University] at 20:17 04 July 2015 forms, it would be disappointing if other such species cannot be detected and characterised spectroscopically in the radio band in the near future.…”

Section: Discussionmentioning

confidence: 95%

High-resolution rotational spectroscopy of iminosilylene, HNSi

2015

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By means of Fourier transform microwave spectroscopy of a supersonic beam, the fundamental rotational transition of isotopic and vibrationally excited iminosilylene, HNSi, has been detected. In addition to seven isotopic species, vibrational satellite transitions from more than 30 vibrationally excited states, including the three fundamental modes, have been detected. Those from ν 2 are particularly intense, enabling detection of transitions from as high as (0,22 0 ,0) (i.e. ∼10,000 cm −1 above ground). At high spectral resolution, well-resolved nitrogen quadrupole structure has been observed in nearly every transition. Excitation of ν 1 or ν 3 changes eQq(N) little, but eQq(N) systematically decreases with increasing excitation of the ν 2 bend, from a value of 0.376(5) MHz for (0,0 0 ,0) to −2.257(5) MHz for (0,20 0 ,0). With the large amount of new data in hand, it has also been possible to determine the leading vibration-rotation constants (α i and γ i ) for ν 2 or ν 3 to high precision, and derive a revised semi-empirical equilibrium structure for this fundamental triatomic molecule. Various electronic and molecular properties of iminosilylene have been calculated at the coupled cluster level of theory, and these generally agree well with experiment and previous calculations. An unsuccessful search for HSiN, a highly polar isomer calculated to lie nearly 3 eV above HNSi, is also reported.

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Section: Discussionmentioning

confidence: 95%

High-resolution rotational spectroscopy of iminosilylene, HNSi

2015

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“…It operates from 5 to 42 GHz, but higher-frequency transitions can often be detected using double resonance (DR) spectroscopy (Jäger & Gerry 1995;Sumiyoshi et al 2005). In this type of experiment (Crabtree et al 2013), the intensity of a line that falls in the operating band of the cavity spectrometer is monitored as a second radiation source is swept in frequency. Normally, this second source propagates perpendicular to the axis of the Fabry-Perot cavity, typically near the beam waist.…”

Section: Methodsmentioning

confidence: 99%

A LABORATORY STUDY OF C ₃ H ⁺ AND THE C ₃ H RADICAL IN THREE NEW VIBRATIONALLY EXCITED ² Σ STATES USING A PIN-HOLE NOZZLE DISCHARGE SOURCE

McCarthy¹,

Crabtree²,

Martin‐Drumel³

et al. 2015

ApJS

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Rotational lines of the positive molecular ion C 3 H + and of the neutral C 3 H radical in three new vibrationally excited states with 2 Σ symmetry have been detected in a supersonic molecular beam in the centimeter-wave band. The fundamental rotational line of the ion is quite weak, but is observed with similar intensity in a dc discharge through several different hydrocarbon gases when helium is the buffer gas. Under these conditions, the fractional abundance of C 3 H + relative to C 3 H is estimated to be of order 10 −4 , i.e., toward the lower end of the ratio (10 −3 -10 −4 ) found for protonated ions using the same discharge nozzle. For each new 2 Σ state of the C 3 H radical, spectroscopic constants, including those describing hydrogen hyperfine structure, have been determined to high precision. Lines of one 2 Σ state (B = 11271 MHz) are particularly intense in our molecular beam; for this state and a second one (B = 11306 MHz), millimeter-wave transitions have also been observed between 180 and 340 GHz using a long path dc glow absorption spectrometer. On the basis of intensity measurements with this spectrometer, the inferred rotation-vibration constant α, and theoretical calculations, the state with B = 11271 MHz is tentatively assigned to the ν 5 bending mode, predicted to lie ∼300 cm −1 above ground.

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“…Because these tools are empirical and unbiased, taken together they can be used to identify highly abundant molecules that have never been the subject of prior experimental or theoretical study. Examples include HNSiN, H 3 NSiN, 102 and HC 4 C(O)H, 103 among others. A recent MST analysis of the discharge chemistry starting from diacetylene and carbon disulfide, for example, resulted in the detection and assignment of more than 85 unique variants, including several new isotopic species and more than 25 new vibrationally excited states of C 2 S, C 3 S, and C 4 S. 104 Perhaps the best illustration of these techniques and one of direct relevance to hydrocarbon chemistry is our recent analysis of a relatively simple system -an electrical discharge of benzene (C 6 H 6 ) alone 105 or in combination with molecular oxygen or nitrogen.…”

Section: Exhaustive Complex Mixture Analysismentioning

confidence: 99%

Aromatics and Cyclic Molecules in Molecular Clouds: A New Dimension of Interstellar Organic Chemistry

McCarthy,

McGuire

2021

Preprint

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Astrochemistry lies at the nexus of astronomy, chemistry, and molecular physics. On the basis of precise laboratory data, a rich collection of more than 200 familiar and exotic molecules have been identified in the interstellar medium, the vast majority by their unique rotational fingerprint. Despite this large body of work, there is scant evidence in the radio band for the basic building blocks of chemistry on earth -five and six-membered rings -despite long standing and sustained efforts during the past 50 years. In contrast, a peculiar structural motif, highly unsaturated carbon in a chain-like arrangement, is instead quite common in space. The recent astronomical detection of cyanobenzene, the simplest aromatic nitrile, in the dark molecular cloud TMC-1, and soon afterwards in additional pre-stellar, and possibly protostellar sources, establishes that aromatic chemistry is likely widespread in the earliest stages of star formation. The subsequent discovery of cyanocyclopentadienes and even cyanonapthlenes in TMC-1 provides further evidence that organic molecules of considerable complexity are readily synthesized in regions with high visual extinction but where the low temperature and pressure are remarkably low. This review focuses on laboratory efforts now underway to understand the rich transition region between linear and planar carbon structures using microwave spectroscopy. We present key features, advantages, and disadvantages of current detection methods, a discussion of the types of molecules found in space and in the laboratory, and approaches under development to identify entirely new species in complex mixtures. Studies focusing on the cyanation of hydrocarbons and the formation of benzene from acyclic precursors are highlighted, as is the role that isotopic studies might play in elucidating the chemical pathways to ring formation.

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Detection of Two Highly Stable Silicon Nitrides: HSiNSi and H₃SiNSi

Cited by 16 publications

References 52 publications

High-resolution rotational spectroscopy of iminosilylene, HNSi

High-resolution rotational spectroscopy of iminosilylene, HNSi

A LABORATORY STUDY OF C ₃ H ⁺ AND THE C ₃ H RADICAL IN THREE NEW VIBRATIONALLY EXCITED ² Σ STATES USING A PIN-HOLE NOZZLE DISCHARGE SOURCE

Aromatics and Cyclic Molecules in Molecular Clouds: A New Dimension of Interstellar Organic Chemistry

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Detection of Two Highly Stable Silicon Nitrides: HSiNSi and H3SiNSi

Cited by 16 publications

References 52 publications

High-resolution rotational spectroscopy of iminosilylene, HNSi

High-resolution rotational spectroscopy of iminosilylene, HNSi

A LABORATORY STUDY OF C 3 H + AND THE C 3 H RADICAL IN THREE NEW VIBRATIONALLY EXCITED 2 Σ STATES USING A PIN-HOLE NOZZLE DISCHARGE SOURCE

Aromatics and Cyclic Molecules in Molecular Clouds: A New Dimension of Interstellar Organic Chemistry

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Detection of Two Highly Stable Silicon Nitrides: HSiNSi and H₃SiNSi

A LABORATORY STUDY OF C ₃ H ⁺ AND THE C ₃ H RADICAL IN THREE NEW VIBRATIONALLY EXCITED ² Σ STATES USING A PIN-HOLE NOZZLE DISCHARGE SOURCE