The fluorescence depletion spectroscopy of CdCH3

Pushkarsky, Michael B.; Barckholtz, Timothy A.; Miller, Terry A.

doi:10.1063/1.477867

Cited by 12 publications

(7 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The primary difference between the LIF and REMPI spectra of MgCH 3 is that the latter reveals the fundamental of ν 3 , which was absent from the former . We have shown elsewhere that many vibrational levels of the excited state of CdCH 3 undergo a rapid, nonradiative process, making them dark to the LIF experiment but observable by a fluorescence depletion technique . The most likely explanation of the observation of ν 3 in the REMPI spectrum, but not in the LIF spectrum, is that its lifetime is sufficiently long for it to be observed in the REMPI spectrum (the two lasers have a temporal width of approximately 5 ns each and are overlapped to within 2 or 3 ns) but short enough that it does not radiate sufficient photons to be observed by the LIF technique.…”

Section: Resultsmentioning

confidence: 95%

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

et al. 1999

Self Cite

View full text Add to dashboard Cite

The resonance-enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectra of the organometallic radicals MgCH3 and ZnCH3 are reported. The radicals were generated in a pulsed supersonic expansion and therefore had vibrational and rotational temperatures of ca. 10 K. The REMPI experiments have resolved the spin−orbit and vibrational structure of the excited state, which is used as an intermediate state in the ZEKE experiment. Because of the intrinsically high resolution of the ZEKE technique, the photoelectron spectra of these radicals were vibrationally resolved. We also report density functional calculations of the geometries and vibrational frequencies of these radicals, and those of the closely related radicals CaCH3 and CdCH3. We have shown how the photoelectron spectra of these radicals can be used to generate high-resolution “experimental” MO diagrams of molecules that contain these fragments. We illustrate this approach with the MO diagram of Zn(CH3)2.

show abstract

Section: Resultsmentioning

confidence: 95%

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

et al. 1999

Self Cite

View full text Add to dashboard Cite

show abstract

“…Over the past two decades, much attention has been paid to molecular clusters and metal−ligand type complexes to link the gap between the gas phase and the condensed one. Various spectroscopic techniques have been applied to newly synthesized complexes to obtain information about energetics, structure, and dynamics. − Bonding character and structure of such complexes are compared with its constituent “free” molecules. − Small size clusters can serve as a model system for observing metal−ligand interaction in an isolated form. Only recently, Jakubek and Simard have performed a ZEKE study of the AlND 3 complex for measuring the ionization potentials and the vibrational frequencies in the excited states .…”

Section: Introductionmentioning

confidence: 99%

Direct Determination of the Permanent Dipole Moments and Structures of Al−CH₃CN and Al−NH₃ by Using a 2-m Electrostatic Hexapole Field

et al. 2001

View full text Add to dashboard Cite

The supersonic beams of the (1-1) metal-ligand complexes of Al-CH(3)CN and Al-NH(3) were produced by a laser evaporation method. Nondestructive structure selection of the complexes and the dipole moment determination were performed by using a 2-m electrostatic hexapole field. The experimentally determined permanent dipole moments are 1.2 +/- 0.1 D for Al-CH(3)CN and 2.7 +/- 0.2 D for Al-NH(3). We find that the dipole moment of Al-NH(3) becomes larger than that of neat NH(3), while the formation of the Al-CH(3)CN complex produces a smaller dipole moment than that of neat CH(3)CN on the other hand. We performed the ab initio calculations to draw out plausible complex structures and to clarify the bonding character after formation of the complex, and we made comparisons with the computational results done by several groups. The Mulliken population analysis suggests the Al-->CH(3)CN charge flow, but on the other hand the Natural population analysis indicates very little charge flow. For the Al-NH(3) complex, the polarization effect of NH(3) and the N-->Al sigma donation would enhance the dipole moment strength. However, there still remains a controversial disagreement between the theoretical predictions and the experimental results. Further experimental determination using the hexapole method for various metal-ligand complexes and clusters could reveal the basic nature of interaction in the complex systems in general, and this method would complement theoretical calculations.

show abstract

“…Finally, we have assigned the previously unassigned band (#7) at 23 602 cm -1 as a symmetric CH 2 /CH 3 wag, 7 1 , based upon ab initio calculations and the intensity pattern in the ZEKE spectra of the cation, as will be discussed below. No strong transitions have been observed at frequencies above 23 600 cm -1 , likely due to poor Franck−Condon factors and/or the opening of a nonradiative process, similar to that observed in CdCH 3 radical . The vibrational information for the ZnC 2 H 5 radical is summarized in the Table I.…”

Section: Resultsmentioning

confidence: 87%

Photoionization Spectroscopy of the Zinc Monoethyl Radical and Its Cation

Pushkarsky¹,

Miller²

2000

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

The spectra of the ZnC 2 H 5 radical and its cation have been recorded by two photoionization techniques, resonantly enhanced multiphoton ionization and zero electron kinetic energy spectroscopy, respectively. The ionization potential of the radical has been determined along with a number of vibrational frequencies in the ground state of the cation and the excited state of the neutral. Based upon the spectroscopic data, models for the metal-carbon bonding in metal alkyl radicals are proposed that predict relative bond strengths for a number of species.

show abstract

The fluorescence depletion spectroscopy of CdCH3

Abstract: Articles you may be interested inHigh-resolution laser spectroscopy and magnetic effect of the B ̃ 2E′ ← X ̃ 2A2′ transition of 14NO3 radical

Cited by 12 publications

References 41 publications

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

Direct Determination of the Permanent Dipole Moments and Structures of Al−CH₃CN and Al−NH₃ by Using a 2-m Electrostatic Hexapole Field

Photoionization Spectroscopy of the Zinc Monoethyl Radical and Its Cation

Contact Info

Product

Resources

About

The fluorescence depletion spectroscopy of CdCH3

Abstract: Articles you may be interested inHigh-resolution laser spectroscopy and magnetic effect of the B ̃ 2E′ ← X ̃ 2A2′ transition of 14NO3 radical

Cited by 12 publications

References 41 publications

ZEKE Spectroscopy of the Organometallic Radicals MgCH3 and ZnCH3: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

ZEKE Spectroscopy of the Organometallic Radicals MgCH3 and ZnCH3: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

Direct Determination of the Permanent Dipole Moments and Structures of Al−CH3CN and Al−NH3 by Using a 2-m Electrostatic Hexapole Field

Photoionization Spectroscopy of the Zinc Monoethyl Radical and Its Cation

Contact Info

Product

Resources

About

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

ZEKE Spectroscopy of the Organometallic Radicals MgCH₃ and ZnCH₃: Construction of a High-Resolution “Experimental” Molecular Orbital Diagram

Direct Determination of the Permanent Dipole Moments and Structures of Al−CH₃CN and Al−NH₃ by Using a 2-m Electrostatic Hexapole Field