A potential energy surface and a trajectory study of photodynamics and strong-field alignment of ClF molecule in rare gas (Ar,Kr) solids

Kiljunen, Toni; Bargheer, Matias; Gühr, Markus; Schwentner, N.

doi:10.1039/b315149b

Cited by 21 publications

(35 citation statements)

References 38 publications

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“…We concentrate solely on the angular degrees of freedom (θ , φ ) of the guest molecule and neglect possible deformations of the matrix in accommodating the impurity. This approximation complements the earlier work [38,[41][42][43][44] where the radial coordinate has played a major role in coupling the guest motions to various host modes.…”

Section: Methodssupporting

confidence: 81%

“…Recently, we studied the ClF molecule (B = 0.5165 cm −1 , ∆ω = 27 at 1 TW/cm 2 field intensity, and ω = 3 at 100 kV/cm field strength) in Refs. [43,44], where also the interaction with the matrix was estimated. Other work giving explicit values of κ can be found from spectroscopy [32,39,[51][52][53] and modelling [35,49,54] of librational states.…”

Section: Discussionmentioning

confidence: 99%

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Aligning and orienting molecules trapped in octahedral crystal fields

2005

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The effect of external fields on directional states of a linear molecule trapped in a crystal field of octahedral symmetry is studied numerically. Adiabatic field-dressed energy levels are obtained by solving the time-independent Schrödinger equation for the rotational degrees of freedom of the confined molecule. In the absence of external fields, the internal, octahedral crystal field serves to transform free-rotor states to angularly confined librational states of defined parity which arrange in near-degenerate sets of high multiplicity. Interaction of a linearly polarized, nonresonant laser field with the polarizability or of a static electric field with the dipole moment create alignment or orientation of the molecular axis, respectively. In the latter case, the combined effect of internal (octahedral) and external static field is instrumental in creating orientation by coupling different tunneling states. Depending on the polarization direction of the external fields with respect to the symmetry axes provided by the crystal field, cooperative and competitive effects are distinguished. If the direction of the external field coincides with the minima of the crystal field, high degrees of alignment or orientation can be achieved for specific states, even for low field strengths. Otherwise, high efficiency of this mechanism is restricted to high fields and low temperatures. Strategies for an experimental realization are outlined.

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Section: Methodssupporting

confidence: 81%

Section: Discussionmentioning

confidence: 99%

Aligning and orienting molecules trapped in octahedral crystal fields

2005

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“…A geminate recombination is forced, if the molecular axis points towards a nearest neighbor atom. 60,61 Furthermore, the direction of the molecular axis is tilted after recombination if the F fragment scatters from the cage in an asymmetric way. Thus, the excitation to the transition state results in a change of the angular coordinate and an ultrafast depolarization of the molecular axis direction 57 (section 4).…”

Section: (Section 3)mentioning

confidence: 99%

“…Indeed, one challenge for theory to reproduce experimental observations lies in a proper description of the potential energy surfaces in the many-body system, which to a large extent dictate the dynamics of the wave packets created. 60,61 A second hotspot for theory lies in treating the quantum nature of the wave packets and the nonadiabatic dynamics in particular. 114 Important trapping sites for molecules appear as single, double, or multi-substitution vacancies, i.e., one, two, or more lattice atom positions are occupied by the impurity molecule.…”

Section: Dissociation Of Clf In Rare Gas Solidsmentioning

confidence: 99%

Ultrafast dynamics of halogens in rare gas solids

Gühr

Bargheer

Fushitani

et al. 2007

Phys. Chem. Chem. Phys.

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We perform time resolved pump-probe spectroscopy on small halogen molecules ClF, Cl2, Br2, and I2 embedded in rare gas solids (RGS). We find that dissociation, angular depolarization, and the decoherence of the molecule is strongly influenced by the cage structure. The well ordered crystalline environment facilitates the modelling of the experimental angular distribution of the molecular axis after the collision with the rare gas cage. The observation of many subsequent vibrational wave packet oscillations allows the construction of anharmonic potentials and indicate a long vibrational coherence time. We control the vibrational wave packet revivals, thereby gaining information about the vibrational decoherence. The coherence times are remarkable larger when compared to the liquid or high pressure gas phase. This fact is attributed to the highly symmetric molecular environment of the RGS. The decoherence and energy relaxation data agree well with a perturbative model for moderate vibrational excitation and follow a classical model in the strong excitation limit. Furthermore, a wave packet interferometry scheme is applied to deduce electronic coherence times. The positions of those cage atoms, excited by the molecular electronic transitions are modulated by long living coherent phonons of the RGS, which we can probe via the molecular charge transfer states.

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“…20,21 As a coherence-based control tool, efficient extension of the alignment mechanism to the condensed phase is posing challenges both experimentally and theoretically. [22][23][24][25] Therefore, parahydrogen (pH 2 ) as a minimally perturbing quantum condensed phase makes natural sense as the media to study.…”

Section: Introductionmentioning

confidence: 99%

A potential energy surface and a trajectory study of photodynamics and strong-field alignment of ClF molecule in rare gas (Ar,Kr) solids

Cited by 21 publications

References 38 publications

Aligning and orienting molecules trapped in octahedral crystal fields

Aligning and orienting molecules trapped in octahedral crystal fields

Ultrafast dynamics of halogens in rare gas solids

Excitation of rotons in parahydrogen crystals: The laser-induced-molecular-alignment mechanism

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