Microwave spectrum, ground state structure, and dipole moment of thioformaldehyde

Johnson, Donald R.; Powell, F. X.; Kirchhoff, William H.

doi:10.1016/0022-2852(71)90284-0

Cited by 215 publications

(50 citation statements)

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“…Although an interstellar search for thioformaldehyde was carried out ( Evans et al 1970) soon after the first microwave laboratory study (Johnson & Powell 1970), the first interstellar detection was reported a few years later (Sinclair et al 1973). Meanwhile, the extension of the known rotational spectrum to higher microwave and millimeter-wave frequencies (Johnson et al 1971;Beers et al 1972) allowed predictions of a large number of unmeasured lines to be made available for interstellar identification of thioformaldehyde . These predictions have proven useful over the years, and currently can be found in the Jet Propulsion Laboratory (JPL) Spectral Line Catalog 2 (Pickett et al 1998).…”

Section: à9mentioning

confidence: 99%

“…The original microwave detection, through 35 GHz, was followed by microwave measurements through 70 GHz, in which mainly Q-branch (ÁJ ¼ 0) transitions were assigned up to J 00 ¼ 27 and K 00 a ¼ 2 (Johnson et al 1971). These authors also studied the 13 C and 34 S isotopologues of thioformaldehyde in order to obtain the molecular structure.…”

Section: à9mentioning

confidence: 99%

“…These authors also studied the 13 C and 34 S isotopologues of thioformaldehyde in order to obtain the molecular structure. Finally, Johnson et al (1971) transitions through J 00 ¼ 6 and K 00 a ¼ 5. The molecular parameters determined from their work, which include one sextic-order centrifugal distortion parameter, allowed frequency predictions through the 300 GHz region with less than 500 kHz error.…”

Section: à9mentioning

confidence: 99%

“…In 2006, one of us (H. S. P. M.) reanalyzed the microwave (Johnson et al 1971;Fabricant et al 1977) and millimeter-wave data ( Beers et al 1972) combined with the far-infrared data ( McNaughton & Bruget 1993) in order to provide more accurate predictions of the rotational spectral lines of thioformaldehyde. The reanalysis was performed carefully by excluding data having residuals more than 3 , and new predictions were provided for thioformaldehyde in its ground vibrational state.…”

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High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State

Maeda

Medvedev

Winnewisser

et al. 2008

ASTROPHYS J SUPPL S

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Pure rotational transitions have been measured for the normal isotopologue of thioformaldehyde, H 12 2 C 32 S, in the ground vibrational state in the 110-370 GHz, 570-670 GHz, and 850-930 GHz frequency ranges. A global data set has been constructed consisting of prior microwave and millimeter-wave transitions, the submillimeter-wave and terahertz (THz) transitions reported here, and far-infrared data and ground state combination differences. The 783 different transition frequencies in the data set were fit to Watson's S-reduced Hamiltonian with 20 parameters, resulting in a dimensionless weighted root-mean-square deviation of 0.78. New frequency predictions have been made for astronomical observations based on the molecular parameters obtained in the present study.

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Section: à9mentioning

confidence: 99%

Section: à9mentioning

confidence: 99%

Section: à9mentioning

confidence: 99%

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confidence: 99%

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High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State

Maeda

Medvedev

Winnewisser

et al. 2008

ASTROPHYS J SUPPL S

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“…22a; for C and H, ref. 22b), STO-3G* (18), 6-31G (21)', and 6-31G* basis sets for the molecules: hydrogen sulfide, methanethiol, thiirane, thioformaldehyde; and thioketene, for which the experimental geometries are known (23)(24)(25).…”

Section: Methodsmentioning

confidence: 99%

Abinitio molecular orbital studies on thiirene and its isomeric structures

Gosavi¹,

Strausz²

1983

Can. J. Chem.

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This article is dedicated to Professor Harry E. Gunning on the occasion of' his 65111 birthclqRATNAKAR K. GOSAVI and OTTO P. STRAUSZ. Can. J. Chem. 61, 2596Chem. 61, (1983. Ab initio molecular orbital calculations have been carried out on the lowest closed shell singlet states of six isomeric forms of CzHIS at the SCF and C1 levels using STO-3G and 6-3 1G" basis sets. Molecular geometries of the isomers and the activatcd complexes for their isomerization reactions were optimized by the energy gradient method at the SCF .level and the C1 calculations were performed at these geometries. In addition, the lowest singlet and triplet states of the. SCHCH diradical were also studied and their geometries optimized by the Restricted Hartree Fock method.The computed stabilities follow the orderThe pseudo antiaromatic character of the 4n-T electron thiirene is manifested by its drastically reduced C-S bond energy, -15 kcal mol-I as compared to the value of >40 kcal mol-' estimated for its 21-1-71. electron analog, thiirane. This explains why thiirenes can be stabilized in inert matrices at 8 K but decompose readily at higher temperatures. In agreement with experimental results the lowest energy path for the unimolecular decomposition of thiirene leads to thioketene via the lowest singlet (or triplet) state of thioformylmethylene.The ir frequencies calculated for thiirene from rib initio mo theory using 6-31'3 + polarization functions on the sulfur show reasonably good agreement with the experimental frequencies, confirming the carlier assignments of the ir spectrum of thiirene. Les stabilites calculCes sont dans I'ordrc suivant:Le caractere pseudo antiaromatique de I'Clectron 41-1-71. du thiirene se manifestc par la reduction drastique de son Cnergie de liaison C-S de = 15 kcal mol-' telle que comparCe 6 la valeur supkrieure 6 40 kcal mol-' CvaluCe pour I'Clectron 211-71. analogue du thiirane. Ceci expIique pourquoi on peut stabiliser les thiirenes dans des matrices inertes 6 8 K mais ils se decomposent rapidement i des tempkratures plus 6levCes. En accord avec les rCsultats expCrimentaux, la voie de plus faible Cnergie pour la dCcomposition unimolCculaire du thiirkne conduit au thiocetkne via I'Ctat singulet (ou triplet) le plus bas du thioformylene.Les frkquences ir calculCes pour le thiirene 6 partir de la theoric ab irlitio des OM utilisant la base 6-31G + les fonctions de polarisation du soufre montrent un accord raisonnablement bon avec les frkqucnces experimentales confirmant ainsi les attributions anterieures du spectre ir du thiirene.[Traduit par le journal]

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The ?, ?* state in formaldehyde and thioformaldehyde

Grein

Hachey

1996

Int. J. Quantum Chem.

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mFor formaldehyde, the C -0 stretch potential of '(T, r*) crosses all 'A, Rydberg \r, r* + 2 system to these Rydberg states. For thioformaldehyde, the situation is similar but a shift in the potentials allows for direct observation of '(r, T * ) . In its ' ( T , T * ) state, H,CO is planar, having a low barrier of about 0.2 eV toward the nonplanar '(v, T * > state. For H,CS, the planar conformation of ' ( T , r*) is a saddle point, with '(v, r*) being the global minimum on the 2'A' surface. The triplet r, r* states of H,CO and H,CS are nonplanar, having inversion barriers of 0.1 and 0.05 eV, respectively. For both H,CO and H,CS, the T , r* configuration also crosses the ground-state configuration, which explains predissociation and radiationless transitions of some Rydberg states.otentials, such as n, 3p,, n, 3d,,, etc., thereby transferring the intensity of the unassigned 0 1996 John Wiley & Sons, Inc.

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Microwave spectrum, ground state structure, and dipole moment of thioformaldehyde

Cited by 215 publications

References 8 publications

High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State

High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State

Abinitio molecular orbital studies on thiirene and its isomeric structures

The ?, ?* state in formaldehyde and thioformaldehyde

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Microwave spectrum, ground state structure, and dipole moment of thioformaldehyde

Cited by 215 publications

References 8 publications

High‐Frequency Rotational Spectrum of Thioformaldehyde, H2CS, in the Ground Vibrational State

High‐Frequency Rotational Spectrum of Thioformaldehyde, H2CS, in the Ground Vibrational State

Abinitio molecular orbital studies on thiirene and its isomeric structures

The ?, ?* state in formaldehyde and thioformaldehyde

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Product

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High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State

High‐Frequency Rotational Spectrum of Thioformaldehyde, H₂CS, in the Ground Vibrational State