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Synchronized flash photolysis and pulse deposition in matrix isolation experiments.
L J Allamandola1, D Lucas, G C Pimentel
1Laboratorium Astrofysica, Huygens Laboratorium, Wassenaarseweg 78, 2300 RA Leiden, The NetherlandsDepartment of Chemistry, Indiana University, Bloomington, Indiana 47401Department of Chemistry, University of California, Berkeley, California 94720.
The Review of Scientific Instruments
|July 1, 1978
Summary
This study introduces a novel flash photolysis apparatus for matrix isolation experiments. The new technique effectively produces and traps transient species like CF(3) and ClCO, improving spectral sensitivity.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Chemical Physics
Background:
- Matrix isolation spectroscopy is crucial for studying unstable molecules.
- Traditional in situ photolysis methods are limited by cage effects and secondary photolysis.
- Transient species require specialized techniques for their generation and detection.
Purpose of the Study:
- To develop an apparatus for flash photolysis of pulse-deposited gas mixtures in matrix isolation.
- To overcome limitations of conventional photolysis techniques.
- To investigate the photolytic decomposition of tricarbonylironcyclobutadiene.
Main Methods:
- Utilizing a pulsed deposition technique with synchronized flashlamps for photolysis.
- Employing infrared spectroscopy for detection of transient species.
- Analyzing the photolytic decomposition products of gaseous tricarbonylironcyclobutadiene (C(4)H(4)Fe(CO)(3)).
Main Results:
- Demonstrated successful production and trapping of trifluoromethyl (CF(3)) and chlorocarbonyl (ClCO) radicals.
- Observed line narrowing in spectra due to pulsed deposition, enhancing sensitivity.
- Identified carbon monoxide (CO) as the primary photolytic elimination product from C(4)H(4)Fe(CO)(3), not cyclobutadiene (C(4)H(4)).
Conclusions:
- The developed flash photolysis apparatus combined with pulsed deposition is effective for generating and trapping transient species.
- This technique offers improved spectral sensitivity and overcomes limitations of prior methods.
- The primary photolytic pathway for tricarbonylironcyclobutadiene involves CO elimination.
