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2006, Physical Review A
We report an experimental study of non-adiabatic laser-induced molecular alignment of ethylene (C2H4) using a linearly polarized short laser pulse of moderate intensity. The information about the confinement of the C=C bond axis along the direction of the applied electric field is obtained by measuring the depolarization of a second short pulse of weak intensity interacting with the molecules after they have been exposed to the first pulse. The experimental data are compared with the numerical simulation of the Schrödinger equation written for the non-resonant interaction of an asymmetric top rigid rotor with a linearly polarized electric field. The field-free alignment is described by analyzing the time evolution of the angular distribution of the molecular axes together with the expectation value of the relevant squared direction cosine matrix elements.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
We review on the theoretical status of intense laser orientation and alignment-a field at the interface between intense laser physics and chemical dynamics with the potential applications ranging from high harmonic generation, nano-scale processing and control of chemical reactions. The evolution of the rotational wave packet and its dynamics leading to orientation and alignment is the topic of the present discussion. The major part of the article basically presents an overview on recent theoretical progress in controlling the orientation and alignment dynamics of a molecule by means of shaped laser pulses. The various theoretical approaches that lead to orientation and alignment ranging from static electrostatic field in combination with laser field(s), combination of orienting and aligning field, combination of aligning fields, combination of orienting fields, application of train of pulses etc. are discussed. It is focussed that the train of pulses proves to be quite efficient in increasing the orientation or alignment of a molecule without causing the molecule to ionize. The orientation and alignment both can occur in adiabatic and non-adiabatic conditions with the rotational
Physical Review Letters, 2005
We show that a linear molecule subjected to a short specific elliptically polarized laser field yields postpulse revivals exhibiting alignment alternatively located along the orthogonal axis and the major axis of the ellipse. The effect is experimentally demonstrated by measuring the optical Kerr effect along two different axes. The conditions ensuring an optimal field-free alternation of high alignments along both directions are derived. 32.80.Lg, 42.50.Hz Preparing controlled alignment of molecules is of considerable importance for a large variety of processes (see [1] for a review). It is well established theoretically and experimentally that the alignment of a linear molecule along the axis of a linearly polarized field can be of two types: adiabatic alignment during the interaction with the field, or transient alignment revivals after a short pulse. The latter is in general preferred for further manipulations since it offers field-free aligned molecules. The adiabatic alignment has been extended to three dimensional alignment of an asymmetric top molecule .
Physical Review Letters, 2001
We examine the time evolution of states created by the nonadiabatic interaction of a polar molecule with combined electrostatic and pulsed nonresonant laser fields and show that the orientation due to the electrostatic field alone can be greatly enhanced by restricting the angular amplitude of the molecule by the pulsed laser field. An analytic model indicates that in the short-pulse limit the interaction is governed by an impulsive transfer of action from the radiative field to the molecule.
Physical Review A, 2005
Quantum-mechanical calculations are performed of the dynamic alignment of linear molecules induced by a strong nonresonant laser field. Within this framework we have treated in a unified fashion the alignment with laser pulses of varying duration from the short pulse impulsive limit ͑ pulse Ӷ T rot ͒ to the long pulse adiabatic limit ͑ pulse Ͼ T rot ͒. The temporal behavior of the alignment in both these limits, and in the intermediate pulse duration regime, have been analyzed. For the impulsive limit the dependence of the degree of maximum alignment upon the laser pulse duration was examined and the intensity-dependent optimum pulse duration explained. A comparison between the degree of alignment under the same conditions of pulse intensity and rotational temperature was performed between the impulsive and adiabatic cases. The adiabatic case was found to always provide a better degree of alignment for a given intensity which we show is due to the zero relative phasing between the component states of the superposition that form the pendular states. We have explicitly calculated the angular distribution of an ensemble of linear molecules as it evolves through a rotational revival; a rich structure is found that may be useful in guiding future experiments that utilize the field free alignment in a revival.
Physical Review A, 2007
An investigation of field-free molecular alignment produced by elliptically polarized laser pulses is reported. Experiments are conducted in CO2 at room temperature. A non invasive all-optical technique, based on the cross defocusing of a probe pulse, is used to measure the alignment along two orthogonal directions that is sufficient to provide a 3 dimensional characterization. The fieldfree molecular alignment produced by a laser of elliptical polarization is in good agreement in terms of amplitude and shape with theoretical predictions. It turns out to be almost equivalent to the superposition of the effects that one would obtain with two individual cross-polarized pulses. The investigation highlights notably the occurrence of field-free two-direction alignment alternation for a suitably chosen degree of ellipticity. The analogy between this specific ellipticity and the well known "magic angle" used in time resolved spectroscopy to prevent rotational contributions is discussed.
We analyze the control of molecular orientation by nonresonant and quasiresonant two-color laser pulses 2+1 process. The laser pulses are assumed to be short with respect to the rotational period. In the nonresonant case, we show that the efficiency of this strategy crucially depends on the polarizability and the hyperpolarizability of the molecule. In the quasiresonant case, i.e., if the 2 frequency is in quasiresonance with a vibrational frequency, one can improve the orientation by adjusting the detuning. The best orientation is obtained for an optimal value of the detuning, which is different from zero
Nature Physics, 2009
Manipulation of the molecular-axis distribution is an important ingredient in experiments aimed at understanding and controlling molecular processes 1-6 . Samples of aligned or oriented molecules can be obtained following the interaction with an intense laser field 7-9 , enabling experiments in the molecular rather than the laboratory frame 10-12 . However, the degree of impulsive molecular orientation and alignment that can be achieved using a single laser field is limited 13 and crucially depends on the initial states, which are thermally populated. Here we report the successful demonstration of a new technique for laser-field-free orientation and alignment of molecules that combines an electrostatic field, non-resonant femtosecond laser excitation 14 and the preparation of state-selected molecules using a hexapole 2 . As a unique quantum-mechanical wavepacket is formed, a large degree of orientation and alignment is observed both during and after the femtosecond laser pulse, which is even further increased (to cos θ = −0.74 and cos 2 θ = 0.82, respectively) by tailoring the shape of the femtosecond laser pulse. This work should enable new applications such as the study of reaction dynamics or collision experiments in the molecular frame, and orbital tomography 11 of heteronuclear molecules.
Physical Review Letters, 2012
We have experimentally and theoretically investigated the mixed-field orientation of rotationalstate-selected OCS molecules and we achieve strong degrees of alignment and orientation. The applied moderately intense nanosecond laser pulses are long enough to adiabatically align molecules. However, in combination with a weak dc electric field, the same laser pulses result in nonadiabatic dynamics in the mixed-field orientation. These observations are fully explained by calculations employing, both, adiabatic and non-adiabatic (time-dependent) models.
Physical Review Letters, 2002
We show that two overlapping linearly polarized laser pulses of frequencies v and its second harmonic 2v can strongly orient linear polar molecules, by adiabatic passage along dressed states. The resulting robust orientation can be interpreted as a laser-induced localization in the effective double well potential created by the fields, which induces a preliminary molecular alignment. The direction of the orientation can be selected by the relative phase of the fields.
Physical Review A, 2001
The propensity of molecules to spatially align along the polarization vector of intense, pulsed light fields is related to readily-accessible parameters (molecular polarizabilities, moment of inertia, peak intensity of the light and its pulse duration). Predictions can now be made of which molecules can be spatially aligned, and under what circumstances, upon irradiation by intense light. Accounting for both enhanced ionization and hyperpolarizability, it is shown that all molecules can be aligned, even those with the smallest static polarizability, when subjected to the shortest available laser pulses (of sufficient intensity).
Collection of Czechoslovak Chemical Communications, 2001
We examine the rotational wavepackets created by the nonadiabatic interaction of a linear molecule with a pulsed nonresonant laser field. We map out the recurrences of the wavepackets and of the concomitant alignment as a function of the duration and intensity of the laser pulse. We derive an analytic solution to the time-dependent Schrödinger equation in the short-pulse limit and find it to agree quantitatively with our numerical computations. This indicates that the recurrences are favored under an impulsive transfer of action from the radiative field to the molecule. The recurring wavepackets afford field-free alignment of the molecular axis.
Physical Review A, 2005
is evaluated for a statistical ensemble of molecules at temperature T distributed according to the Boltzmann weights J 0 , where ͗cos 2 ͘ J 0 ,M 0 ͑t͒ corresponds to a molecule initially in the state labeled by the rotational and magnetic quantum numbers ͉J 0 , M 0 ͘. One can calculate the quantity characterizing the alignment
The Journal of Chemical Physics, 2004
We investigate by numerical simulations the dynamics of alignment of linear molecules in resonant pulsed laser fields and its dependence on pulse length, field strength, and molecular parameters. We propose an analytical short-time approximation for the time-dependent wave packets. We provide a theoretical basis for the occurrence of saturation in the rotational pumping. We present a formula to predict the time at which the maximum alignment occurs. We discuss the magnitude of the laser-induced alignment and we relate it to a theoretical upper limit.
Physical Review A, 2009
We describe theoretically and experimentally a laser-based method to control the rotations of asymmetric top molecules in three-dimensional space. Our method relies on keeping one axis of a molecule essentially fixed in space along the polarization vector of a nanosecond laser pulse ͑termed the long pulse͒ and forcing the molecule to rotate about the aligned axis by an orthogonally polarized, femtosecond laser pulse ͑termed the short pulse͒. Experimentally, we use femtosecond timed Coulomb explosion to image the three-dimensional ͑3D͒ alignment of the 3,5-difluoroiodobenzene molecule as a function of time after the short pulse. Strong 3D alignment is observed a few picoseconds after the short pulse and is repeated periodically, reflecting directly the revolution of the molecular plane about the aligned axis. Our numerical results, based on nonperturbative solution of the time-dependent Schrödinger equation, are in good agreement with the experimental findings and serve to unravel the underlying physical mechanism of the observations. The experiments and theory explore the influence of the laser parameters on the rotational control, in particular the role played by the intensity of the long and the short laser pulses. To illustrate the generality of our method, we illustrate its applicability to a molecule ͑3,4-dibromothiophene͒, with significantly different inertia and polarizability tensors. Finally, our theory shows that the strong 3D alignment obtained by the combined laser pulse method can be converted in to field-free alignment by rapid truncation of the long laser pulse.
Physical Review A, 2007
is evaluated for a statistical ensemble of molecules at temperature T distributed according to the Boltzmann weights J 0 , where ͗cos 2 ͘ J 0 ,M 0 ͑t͒ corresponds to a molecule initially in the state labeled by the rotational and magnetic quantum numbers ͉J 0 , M 0 ͘. One can calculate the quantity characterizing the alignment
The Journal of Physical Chemistry A, 2003
The alignment and molecular structure deformations induced by intense off-resonance excitation with ultrafast laser pulses are examined using femtosecond transient grating spectroscopy and by angle resolved multiphoton ionization in a molecular beam. The goal of this study is to correlate evidence obtained from the angular dependence of multiphoton ionization and from rotational recurrences observed in neutral molecules regarding alignment and molecular structure deformation. Structural parameters are determined by analysis of the fieldfree rotational recurrences, obtained by transient grating measurements, or by analysis of the anisotropy in the detected fragment ions, in the molecular beam experiments. Experimental data were obtained for CS 2 , CO 2 , acetylene, and benzene, for pulse intensities ranging from 10 11 to 10 14 W/cm 2. The experimental results are consistent with molecular alignment resulting from a "kick" induced by the ultrafast off-resonance field. The results also provide evidence of molecular structure deformations. Results from transient grating experiments indicate that the electric field can induce alignment and bending in polyatomic molecules and that these effects can take place in the absence of ionization.
We investigate the effects of delayed infrared laser (IRL) pulse shape on the non-adiabatic rotational excitation and alignment of a polar molecule. We suggest a control scheme for choosing populations of molecular rotational states by wave packet interference. The rotational wave packets of polar molecule (here HBr) excited non-adiabatically by orienting pulse is controlled actually using the second delayed IRL pulse. By adjusting the time delay between the two laser pulses and the shape of delayed IRL pulse, constructive or destructive interference among these wave packets enables the population to be enhanced or repressed for the specific rotational state. We have used fourth order Runge–Kutta method to study the non-adiabatic rotational excitation (NAREX) dynamics.
The Journal of Physical Chemistry A, 2008
The alignment of polyatomic molecules under strong 35 ps laser irradiation is investigated for a broad range of laser intensities (10 13 -10 15 W/cm 2 ) using time-of-flight mass spectrometry. The dynamic alignment of the molecules under study (C 2 H 5 X, X ) I, Br, Cl) is verified in single-pulse experiments by recording the fragments' angular distributions, their dependence on the laser intensity, and also the comparison of the ionic signal of the various fragments recorded for linear and circular polarization. For all cases, the angular distributions of the Coulomb explosion fragments are found to be independent of the laser peak intensity, implying that the molecular alignment is taking place during the rise time of the laser pulses at relatively low intensities (10 13 W/cm 2 ). Moreover, the same result implies that the alignment mechanism is close to the adiabatic limit, albeit the laser pulse duration is much shorter than the characteristic rotational times (1/2B) of the molecules under study. Finally, by comparing the angular distributions of the different molecules, we conclude that the degree of alignment is only weakly dependent on the molecular mass and the moment of inertia under the irradiation conditions applied.
The Journal of Chemical Physics, 2007
The authors show that polar molecules can be adiabatically aligned and oriented by laser pulses more efficiently when the laser frequencies are vibrationally resonant. The aligned molecules are found in a superposition of vibrational pendular states, each associated with the alignment of the rotor in one vibrational state. The authors construct the dressed potential associated with this mechanism. Values of detunings and field amplitudes are given to optimize the degree of alignment and orientation for the CO molecule.
Scientific Reports, 2022
Increasing interest in the fields of high-harmonics generation, laser-induced chemical reactions, and molecular imaging of gaseous targets demands high molecular "alignment" and "orientation" (A&O). In this work, we examine the critical role of different pulse parameters on the field-free A&O dynamics of the CH 3 F molecule, and identify experimentally feasible optical and THz range laser parameters that ensure maximal A&O for such molecules. Herein, apart from rotational temperature, we investigate effects of varying pulse parameters such as, pulse duration, intensity, frequency, and carrier envelop phase (CEP). By analyzing the interplay between laser pulse parameters and the resulting rotational population distribution, the origin of specific A&O dynamics was addressed. We could identify two qualitatively different A&O behaviors and revealed their connection with the pulse parameters and the population of excited rotational states. We report here the highest alignment of �cos 2 θ � = 0.843 and orientation of �cos(θ)� = 0.886 for CH 3 F molecule at 2 K using a single pulse. Our study should be useful to understand different aspects of laser-induced unidirectional rotation in heteronuclear molecules, and in understanding routes to tune/enhance A&O in laboratory conditions for advanced applications. Molecular alignment and orientation (A&O) is essential in the fields of ultrafast science, molecular imaging, time-dependent spectroscopy and detailed interrogation of molecular dynamics 1. Laser-induced field-free or sudden molecular alignment of gas-phase molecules can result in a highly peaked angular distribution of the rotational wavepacket 2 , and it plays an important role in improving the output signal quality of studies that are sensitive to the angle between the molecule and the direction of polarization of the laser field 3,4 , such as high harmonic generation 5,6 , strong field ionization 7 , laser-induced reactions 8 , time-dependent spectroscopy 9 , attosecond pulse shaping 10 , and molecular orbital tomography 11. Many theoretical and experimental efforts 12-14 are reported towards understanding and controlling the non-adiabatic and adiabatic A&O dynamics of molecules with different symmetry. To list a few, the intermediate alignment regime, i.e., the duration of the laser pulse in between the adiabatic and sudden limits, was investigated by Ortigoso et al. 15 , Torres et al. 3 and Seideman et al. 16. Alignment dynamics of different systems with varying individual pulse parameter such as, effect of pulse intensity was studied for the iodobenzene molecule by Lotte Holmegaard et al. 17 , and for the O 2 and N 2 molecules by Peng 18. Bert et al. 19 illustrated the time-resolved rotational dynamics in CO 2 gas after excitation with a single linearly polarized laser pulse, and unidirectional molecular rotation induced by a pulse with twisted polarization. Mizuse et al. 20 reported high-precision time-resolved Coulomb explosion imaging of the rotational wave packets induced by a polarization-skewed double-pulse to investigate the creation process and dynamics of the packets in N 2 molecules. Liu et al. 21 investigated effects of the characteristics of molecules and external fields on field-free molecular orientation, through the comparison of HBr with LiH driven by the combination of a two-color laser pulse and a time-delayed THz laser pulse.
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