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 like TMS do not exhibit a prominent molecular ion (TMS + ) as unimolecular dissociation into [Si(CH 3 ) 3 ] + proceeds very fast. Under 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 wavepacket. The timedependence of this bond hardening process is verified using longer-duration (≥ 100 fs) pulses; the relatively "slower" fall-off of optical field in such pulses allows the initially trapped wavepacket to leak out, thereby rendering TMS + unstable once again. Our results are significant as they demonstrate (i) optical generation of polyatomic ions that are normally inaccessible and (ii) optical control of dynamics in strong fields, with distinct advantages over weak-field control scenarios that demand a narrow bandwidth appropriate for a specified transition.

Carrier-envelope-phase- (CEP) stabilized 5 and 22 fs pulses of intense 800 nm light are used to probe the strong-field ionization dynamics of xenon and carbon disulfide. We compare ion yields obtained with and without CEP stabilization. With 8-cycle (22 fs) pulses, Xe(6+) yields are suppressed (relative to Xe(+)) by 30%-50%, depending on phase, reflecting the phase dependence of nonsequential ionization and its contribution to the formation of higher charge states. Ion yields for Xe(q+) (q = 2-4) with CEP-stabilized pulses are enhanced (by up to 50%) compared to those with CEP-unstabilized pulses. Such enhancement is particularly pronounced with 2-cycle (5 fs) pulses and is distinctly phase dependent. Orbital shape and symmetry affect how CS(2) responds to variations in optical field that are effected as CEP is altered, keeping intensity constant. Molecular fragmentation is found to depend on field strength (not intensity); the relative enhancement of fragmentation when CEP-stabilized 2-cycle pulses are used is found to be at the expense of molecular ionization.

One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O-H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD(+), and HOD(2+) and explorations of the dissociation limits resulting from either O-H or O-D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

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