High-resolution spectroscopy of CoS (X 4 Δ i): Examining 3d transition-metal sulfide bonds

M. A. Flory, S. K. McLamarrah, Lucy M Ziurys

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The pure rotational spectrum of CoS, the cobalt sulfide radical, has been measured using direct absorption techniques in the frequency range of 180-540 GHz. This study is the first spectroscopic investigation of any kind of this molecule. CoS was created by reacting cobalt vapor with H2 S. Four spin components were identified in the spectra of this species, one of which exhibited lambda doubling, identifying the ground state as Δi4. Transitions arising from the lowest spin component of the less abundant Co S34 isotopomer have also been detected, as well as from v=1 and v=2 of the main species. The spectra were readily identified because each spin component exhibited an octet pattern arising from the Co59 spin of I=72. The data were fit using Hund's case (a) Hamiltonian, and rotational, fine-structure, hyperfine, and lambda-doubling constants were determined. The hyperfine parameters support a δ3 π 2 electron configuration and are consistent with some orbital overlap between the metal and sulfur atoms. From the rotational constant, the bond length of CoS was calculated to be r0 =1.977 985 06 (10) Å. This bond length is significantly shorter than that of MnS or FeS, in contrast to the bond distances found in the oxide analogs which are all similar in value. These results indicate that the 3d metal sulfides differ somewhat from their oxide counterparts, probably due to the availability of sulfur p orbitals for bonding.

Original languageEnglish (US)
Article number164312
JournalThe Journal of Chemical Physics
Volume123
Issue number16
DOIs
StatePublished - 2005

Fingerprint

Bond length
Sulfides
Sulfur
Oxides
Transition metals
sulfides
Metals
transition metals
Spectroscopy
Hamiltonians
high resolution
Electron transitions
Cobalt
Ground state
spectroscopy
sulfur
cobalt
Vapors
Availability
orbitals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

High-resolution spectroscopy of CoS (X 4 Δ i) : Examining 3d transition-metal sulfide bonds. / Flory, M. A.; McLamarrah, S. K.; Ziurys, Lucy M.

In: The Journal of Chemical Physics, Vol. 123, No. 16, 164312, 2005.

Research output: Contribution to journalArticle

@article{aa61433935704c43b4c4697a84b482c3,
title = "High-resolution spectroscopy of CoS (X 4 Δ i): Examining 3d transition-metal sulfide bonds",
abstract = "The pure rotational spectrum of CoS, the cobalt sulfide radical, has been measured using direct absorption techniques in the frequency range of 180-540 GHz. This study is the first spectroscopic investigation of any kind of this molecule. CoS was created by reacting cobalt vapor with H2 S. Four spin components were identified in the spectra of this species, one of which exhibited lambda doubling, identifying the ground state as Δi4. Transitions arising from the lowest spin component of the less abundant Co S34 isotopomer have also been detected, as well as from v=1 and v=2 of the main species. The spectra were readily identified because each spin component exhibited an octet pattern arising from the Co59 spin of I=72. The data were fit using Hund's case (a) Hamiltonian, and rotational, fine-structure, hyperfine, and lambda-doubling constants were determined. The hyperfine parameters support a δ3 π 2 electron configuration and are consistent with some orbital overlap between the metal and sulfur atoms. From the rotational constant, the bond length of CoS was calculated to be r0 =1.977 985 06 (10) {\AA}. This bond length is significantly shorter than that of MnS or FeS, in contrast to the bond distances found in the oxide analogs which are all similar in value. These results indicate that the 3d metal sulfides differ somewhat from their oxide counterparts, probably due to the availability of sulfur p orbitals for bonding.",
author = "Flory, {M. A.} and McLamarrah, {S. K.} and Ziurys, {Lucy M}",
year = "2005",
doi = "10.1063/1.2083507",
language = "English (US)",
volume = "123",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "16",

}

TY - JOUR

T1 - High-resolution spectroscopy of CoS (X 4 Δ i)

T2 - Examining 3d transition-metal sulfide bonds

AU - Flory, M. A.

AU - McLamarrah, S. K.

AU - Ziurys, Lucy M

PY - 2005

Y1 - 2005

N2 - The pure rotational spectrum of CoS, the cobalt sulfide radical, has been measured using direct absorption techniques in the frequency range of 180-540 GHz. This study is the first spectroscopic investigation of any kind of this molecule. CoS was created by reacting cobalt vapor with H2 S. Four spin components were identified in the spectra of this species, one of which exhibited lambda doubling, identifying the ground state as Δi4. Transitions arising from the lowest spin component of the less abundant Co S34 isotopomer have also been detected, as well as from v=1 and v=2 of the main species. The spectra were readily identified because each spin component exhibited an octet pattern arising from the Co59 spin of I=72. The data were fit using Hund's case (a) Hamiltonian, and rotational, fine-structure, hyperfine, and lambda-doubling constants were determined. The hyperfine parameters support a δ3 π 2 electron configuration and are consistent with some orbital overlap between the metal and sulfur atoms. From the rotational constant, the bond length of CoS was calculated to be r0 =1.977 985 06 (10) Å. This bond length is significantly shorter than that of MnS or FeS, in contrast to the bond distances found in the oxide analogs which are all similar in value. These results indicate that the 3d metal sulfides differ somewhat from their oxide counterparts, probably due to the availability of sulfur p orbitals for bonding.

AB - The pure rotational spectrum of CoS, the cobalt sulfide radical, has been measured using direct absorption techniques in the frequency range of 180-540 GHz. This study is the first spectroscopic investigation of any kind of this molecule. CoS was created by reacting cobalt vapor with H2 S. Four spin components were identified in the spectra of this species, one of which exhibited lambda doubling, identifying the ground state as Δi4. Transitions arising from the lowest spin component of the less abundant Co S34 isotopomer have also been detected, as well as from v=1 and v=2 of the main species. The spectra were readily identified because each spin component exhibited an octet pattern arising from the Co59 spin of I=72. The data were fit using Hund's case (a) Hamiltonian, and rotational, fine-structure, hyperfine, and lambda-doubling constants were determined. The hyperfine parameters support a δ3 π 2 electron configuration and are consistent with some orbital overlap between the metal and sulfur atoms. From the rotational constant, the bond length of CoS was calculated to be r0 =1.977 985 06 (10) Å. This bond length is significantly shorter than that of MnS or FeS, in contrast to the bond distances found in the oxide analogs which are all similar in value. These results indicate that the 3d metal sulfides differ somewhat from their oxide counterparts, probably due to the availability of sulfur p orbitals for bonding.

UR - http://www.scopus.com/inward/record.url?scp=27344457623&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=27344457623&partnerID=8YFLogxK

U2 - 10.1063/1.2083507

DO - 10.1063/1.2083507

M3 - Article

AN - SCOPUS:27344457623

VL - 123

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 16

M1 - 164312

ER -