A search for the sulphur hexafluoride cation with intense, few cycle laser pulses

It is well established that upon ionization of sulphur hexafluoride, the SF6(+) ion is never observed in mass spectra. Recent work with ultrashort intense laser pulses has offered indications that when strong optical field are used, the resulting "bond hardening" can induce changes in the...

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Bibliographic Details
Published in:The Journal of chemical physics 2013-11, Vol.139 (19), p.194302-194302
Main Authors: Dota, Krithika, Dharmadhikari, Aditya K, Dharmadhikari, Jayashree A, Patra, Kaustuv, Tiwari, Ashwani K, Mathur, Deepak
Format: Article
Language:English
Subjects:
CALCULATION METHODS
CATIONS
Charging
Fluorine
FLUORINE IONS
HARMONIC GENERATION
Harmonic generations
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Ionization
Ions
KINETIC ENERGY
LASERS
MASS SPECTRA
Mass spectrometry
MASS SPECTROSCOPY
MOLECULAR IONS
Organic chemistry
POTENTIAL ENERGY
PULSES
Quantum chemistry
Searching
SULFUR
SULFUR FLUORIDES
Sulfur hexafluoride
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Summary:It is well established that upon ionization of sulphur hexafluoride, the SF6(+) ion is never observed in mass spectra. Recent work with ultrashort intense laser pulses has offered indications that when strong optical field are used, the resulting "bond hardening" can induce changes in the potential energy surfaces of molecular cations such that molecular ions that are normally unstable may, indeed, become metastable enough to enable their detection by mass spectrometry. Do intense, ultrashort laser pulses permit formation of SF6(+)? We have utilized intense pulses of 5 fs, 11 fs, and 22 fs to explore this possibility. Our results are negative: no evidence is discovered for SF6(+). However, multiply charged sulphur and fluorine ions from highly charged SF6(q+) ions are observed that enable us to resolve the controversy regarding the kinetic energy release accompanying formation of F(+) fragment ions. Quantum chemical computations of field-distorted potential energy curves of SF6 and its molecular ion enable us to rationalize our non-observation of SF6(+). Our findings have implications for high harmonic generation from SF6 in the few-cycle regime.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4830222