Vibronic spectroscopy of unsaturated transition metal complexes: CrC2H, CrCH3, and NiCH3

Brugh, Dale J.; DaBell, Ryan S.; Morse, Michael D.

doi:10.1063/1.1821497

Cited by 23 publications

(29 citation statements)

References 61 publications

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“…24,26 The ground state of CrCCH is 6 Σ + . As illustrated in Figure 4, each rotational level for this term, indicated by N, is split into six fine structure components, labeled by J.…”

Section: Resultsmentioning

confidence: 99%

“…23 Vibrationally resolved spectra of NiCH 3 has also been recorded. 24 Spectroscopic studies of chromium-bearing molecules have been almost exclusively the work of Morse and collaborators. These authors have recorded vibrationally resolved spectra of the 6Ẽ -X 6 A 1 transition of CrCH 3 and thẽ A 6 Σ + -X 6 Σ + system of CrCCH 24 using resonant two-photon ionization (R2PI) methods; they also measured the 3 Σ − -X 3 Σ − system of CrC with rotational resolution.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Millimeter-wave spectroscopy of CrC (X3Σ−) and CrCCH (X̃ 6Σ+): Examining the chromium-carbon bond

Min

Ziurys

2016

The Journal of Chemical Physics

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Pure rotational spectroscopy of the CrC (X3Σ−) and CrCCH (X̃ 6Σ+) radicals has been conducted using millimeter/sub-millimeter direct absorption methods in the frequency range 225-585 GHz. These species were created in an AC discharge of Cr(CO)6 and either methane or acetylene, diluted in argon. Spectra of the CrCCD were also recorded for the first time using deuterated acetylene as the carbon precursor. Seven rotational transitions of CrC were measured, each consisting of three widely spaced, fine structure components, arising from spin-spin and spin-rotation interactions. Eleven rotational transitions were recorded for CrCCH and five for CrCCD; each transition in these cases was composed of a distinct fine structure sextet. These measurements confirm the respective 3Σ− and 6Σ+ ground electronic states of these radicals, as indicated from optical studies. The data were analyzed using a Hund’s case (b) Hamiltonian, and rotational, spin-spin, and spin-rotation constants have been accurately determined for all three species. The spectroscopic parameters for CrC were significantly revised from previous optical work, while those for CrCCH are in excellent agreement; completely new constants were established for CrCCD. The chromium-carbon bond length for CrC was calculated to be 1.631 Å, while that in CrCCH was found to be rCr—C = 1.993 Å — significantly longer. This result suggests that a single Cr—C bond is present in CrCCH, preserving the acetylenic structure of the ligand, while a triple bond exists in CrC. Analysis of the spin constants suggests that CrC has a nearby excited 1Σ+ state lying ∼16 900 cm−1 higher in energy, and CrCCH has a 6Π excited state with E ∼ 4800 cm−1.

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“…24,26 The ground state of CrCCH is 6 Σ + . As illustrated in Figure 4, each rotational level for this term, indicated by N, is split into six fine structure components, labeled by J.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Millimeter-wave spectroscopy of CrC (X3Σ−) and CrCCH (X̃ 6Σ+): Examining the chromium-carbon bond

Min

Ziurys

2016

The Journal of Chemical Physics

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“…Simultaneously, C2H radical prefer to maintain its integrity when C 2 H radical interacts with Fe, Cr, Yb, Co and Au [25,26,[27][28][29].…”

Section: Isomers C-h Rocking Vibration C-c Stretching Vibration C-h Smentioning

confidence: 99%

“…High-level ab initio calculations, using the CPd-G2 thaw and CP-G2 composite computational procedures (combined with spin projection techniques when appropriate), are used to explore the bonding between the metal mono cations Na . Brugh [26] found that both the ground and the excited state of CrC 2 H had liner structure and their vibronic spectrum were complicated in the 11100-13300 cm −1 region. The first spectroscopic identification and characterization of YbC 2 H has been reported by combining resonance-enhanced two photon ionization, laser-induced fluorescence and photoionization efficiency spectroscopy with density functional calculations [27].…”

Section: Introductionmentioning

confidence: 99%

A Density-Functional Study on the Interaction of C2H Radical with Silver Clusters Agn0/-(n =1–4)

Xu¹,

Li²,

Song³

et al. 2013

J Chem Eng Process Technol

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The interaction between C 2 H radical and silver clusters Ag n 0/-(n=1-4) has been studied based on a systematic density functional theory (DFT) investigation. The DFT calculated results show that C 2 H radical inclines to interact with silver clusters Ag n 0/-(n =1-4) as an integrity in the most stable structures of C 2 HAg n 0/-(n=1-4) rather than being divided by Ag n clusters. The Ag n 0/-(n =1-4) clusters remain their structural integrities as units in the ground states of C 2 HAg n 0/-(n=1-4). Detailed natural resonance theory (NRT) and natural bond order analyses show that the interaction between the C 2 H radical and the Ag n 0/-(n =1-4) in the most stable structures of C 2 HAg n 0/-(n = 1-4) are mainly ionic. Compared with that of C 2 H radical and the Au n 0/-(n = 1-4), the electronic component in C 2 HAg n 0/-(n = 1-4) increased due to the strong relativistic effects of Au. The stretching vibrational frequencies of C≡C and C-H in the ground states of C 2 HAg n 0/-(n =1-4) occur red shifts compared with those of the C 2 H radical due to the interaction between the Ag n 0/-clusters and C2H radical. The photoelectron spectra (PES) of the most stable structures of C 2 HAg n 0/-(n=1-4) have been simulated to facilitate their future experimental characterizations.

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“…In addition, 53 lines of the 0-0 band of the A-X system of the minor isotopomer 50 CrH (natural abundance 4.3%) were recorded during an investigation of the related CrC 2 H molecule, and these are reported here as well. The study of CrC 2 H has been published elsewhere ( Brugh et al 2004). …”

Section: Introductionmentioning

confidence: 99%

Radiative Lifetime of thev = 0, 1 Levels of the \documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \usepackage[OT2,OT1]{fontenc} \newcommand\cyr{ \renewcommand\rmdefault{wncyr} \renewcommand\sfdefault{wncyss} \renewcommand\encodingdefault{OT2} \normalfont \selectfont} \DeclareTextFontCommand{\textcyr}{\cyr}

Shin

Brugh

Morse

2005

ApJ

Self Cite

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The time-delayed resonant two-photon ionization method has been used to measure the radiative lifetimes of the v ¼ 0 and 1 levels of the A 6 AE þ state of CrH, yielding values of 0:939 AE 0:019 and 1:027 AE 0:066 s, respectively (1 error limits). These measured lifetimes are about 16%-45% longer than those obtained in recent ab initio calculations, a result that is important for modeling of the atmospheric concentration of CrH in the class of substellar objects known as brown dwarfs. Based on these results, it is suggested that the line strengths used to calculate the opacity function used by astronomers should be reduced by a factor of 0.799. In addition, line positions are reported for the 0-0 band of the A 6 AE þ X 6 AE þ system of the minor isotope 50 CrH, along with a least-squares fit of the lines to the standard matrix Hamiltonian.

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Vibronic spectroscopy of unsaturated transition metal complexes: CrC2H, CrCH3, and NiCH3

Cited by 23 publications

References 61 publications

Millimeter-wave spectroscopy of CrC (X3Σ−) and CrCCH (X̃ 6Σ+): Examining the chromium-carbon bond

Millimeter-wave spectroscopy of CrC (X3Σ−) and CrCCH (X̃ 6Σ+): Examining the chromium-carbon bond

A Density-Functional Study on the Interaction of C2H Radical with Silver Clusters Agn0/-(n =1–4)

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