A time-dependent bond-hardening process is discovered in a polyatomic molecule (tetramethyl silane, TMS) using few-cycle pulses of intense 800 nm light. In conventional mass spectrometry, symmetrical molecules such as TMS do not exhibit a prominent molecular ion (TMS(+)) as unimolecular dissociation into [Si(CH(3))(3)](+) proceeds very fast. Under a strong field and few-cycle conditions, this dissociation channel is defeated by time-dependent bond hardening: a field-induced potential well is created in the TMS(+) potential energy curve that effectively traps a wave packet. The time dependence of this bond-hardening process is verified using longer-duration (≥100 fs) pulses; the relatively slower falloff of optical field in such pulses allows the initially trapped wave packet to leak out, thereby rendering TMS(+) unstable once again.
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| http://dx.doi.org/10.1103/PhysRevLett.108.073602 | DOI Listing |
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