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Register a new userState- and molecule-selective rotational control in gas mixtures with a shaped optical centrifuge
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We demonstrate experimentally a method of all-optical selective rotational control in gas mixtures. Using an optical centrifuge - an intense laser pulse whose linear polarization rotates at an accelerated rate, we simultaneously excite two different molecular species to two different rotational frequencies of choice. The new level of control is achieved by shaping the centrifuge spectrum according to the rotational spectra of the centrifuged molecules. The shaped optical centrifuge releases one molecular species earlier than the other, therefore separating their target rotational frequencies and corresponding rotational states. The technique will expand the utility of rotational control in the studies of the effects of molecular rotation on collisions and chemical reactions.
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We use an optical centrifuge to excite coherent rotational wave packets in N$_2$O, CS$_2$ and OCS molecules with rotational quantum numbers reaching up to J=465, 690 and 1186, respectively. Time-resolved rotational spectroscopy at such ultra-high levels of rotational excitation can be used as a sensitive tool to probe the molecular potential energy surface at inter-nuclear distances far from their equilibrium values. Significant bond stretching in the centrifuged molecules results in the growing period of the rotational revivals, which are experimentally detected using coherent Raman scattering. We measure the revival period as a function of the centrifuge-induced rotational frequency and compare it with the numerical calculations based on the known Morse-cosine potentials.
A proof-of-concept framework for identifying molecules of unknown elemental composition and structure using experimental rotational data and probabilistic deep learning is presented. Using a minimal set of input data determined experimentally, we describe four neural network architectures that yield information to assist in the identification of an unknown molecule. The first architecture translates spectroscopic parameters into Coulomb matrix eigenspectra, as a method of recovering chemical and structural information encoded in the rotational spectrum. The eigenspectrum is subsequently used by three deep learning networks to constrain the range of stoichiometries, generate SMILES strings, and predict the most likely functional groups present in the molecule. In each model, we utilize dropout layers as an approximation to Bayesian sampling, which subsequently generates probabilistic predictions from otherwise deterministic models. These models are trained on a modestly sized theoretical dataset comprising ${sim}$83,000 unique organic molecules (between 18 and 180 amu) optimized at the $omega$B97X-D/6-31+G(d) level of theory where the theoretical uncertainty of the spectroscopic constants are well understood and used to further augment training. Since chemical and structural properties depend highly on molecular composition, we divided the dataset into four groups corresponding to pure hydrocarbons, oxygen-bearing, nitrogen-bearing, and both oxygen- and nitrogen-bearing species, training each type of network with one of these categories thus creating experts within each domain of molecules. We demonstrate how these models can then be used for practical inference on four molecules, and discuss both the strengths and shortcomings of our approach, and the future directions these architectures can take.
Strong laser-induced magnetization of oxygen gas at room temperature and atmospheric pressure is achieved experimentally on the sub-nanosecond time scale. The method is based on controlling the electronic spin of paramagnetic molecules by means of manipulating their rotation with an optical centrifuge. Spin-rotational coupling results in high degree of spin polarization on the order of one Bohr magneton per centrifuged molecule. Owing to the non-resonant interaction with the laser pulses, the demonstrated technique is applicable to a broad class of paramagnetic rotors. Executed in a high-density gas, it may offer an efficient way of generating macroscopic magnetic fields remotely (as shown in this work), producing large amount of polarized electrons and converting electronic to nuclear spin polarization.
We report on the first experimental demonstration of enantioselective rotational control of chiral molecules with a laser field. In our experiments, two enantiomers of propylene oxide are brought to accelerated unidirectional rotation by means of an optical centrifuge. Using Coulomb explosion imaging, we show that the centrifuged molecules acquire preferential orientation perpendicular to the plane of rotation, and that the direction of this orientation depends on the relative handedness of the enantiomer and the rotating centrifuge field. The observed effect is in agreement with theoretical predictions and is reproduced in numerical simulations of the centrifuge excitation followed by Coulomb explosion of the centrifuged molecules. The demonstrated technique opens new avenues in optical enantioselective control of chiral molecules with a plethora of potential applications in differentiation, separation and purification of chiral mixtures.
Two-photon excitation (TPE) proceeds via a virtual pathway, which depends on the accessibility of one or more intermediate states, and, in the case of non-centrosymmetric molecules, an additional dipole pathway involving the off-resonance dipole-allowed one-photon transitions and the change in the permanent dipole moment between the initial and final states. Here, we control the quantum interference between these two optical excitation pathways by using phase-shaped femtosecond laser pulses. We find enhancements by a factor of up to 1.75 in the two-photon-excited fluorescence of the photobase FR0-SB in methanol after taking into account the longer pulse duration of the shaped laser pulses. Simulations taking into account the different responses of the virtual and dipole pathways to external fields and the effect of pulse shaping on two-photon transitions are found to be in good agreement with our experimental measurements. The observed quantum control of TPE in condensed phase may lead to enhanced signal at a lower intensity in two-photon microscopy, multiphoton-excited photoreagents, and novel spectroscopic techniques that are sensitive to the magnitude of the contributions from the virtual and dipole pathways to multiphoton excitations.
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