Absorption coefficients and scattering losses of TGG, TGP, KTF, FS, and CeF3 magneto-optical crystals in the visible via cavity ring-down spectroscopy.

We demonstrate a method for determining small absorption coefficients and surface-scattering losses of crystals using cavity ring-down spectroscopy and perform measurements on magneto-optical crystals of terbium gallium garnet (TGG), terbium gallium phosphate (TGP), fused silica (FS), potassium terbium fluoride (KTF), and C e F 3 at 532 and 634 nm. Surface scattering is distinguished from absorption losses by using crystals of different lengths. A figure of merit (FoM) for magneto-optical crystals is defined to evaluate their suitability as intracavity optics in optical cavity applications. It is found that TGP has the highest FoM for crystal lengths up to ∼10m m, whereas C e F 3 and FS potentially outperform TGP for longer crystals. Single-pass applications are also briefly discussed.

A nanosecond-resolved atomic hydrogen magnetometer.

We introduce a novel and sensitive ns-resolved atomic magnetometer, which is at least three orders of magnitude faster than conventional magnetometers. We use the magnetic field dependence of the hyperfine beating of high-density spin-polarized H atoms, produced from the rapid photodissociation of HCl gas with sub-ns laser pulses and measured with a pick-up coil, to demonstrate ns-resolved magnetometry, and project sensitivity of a few nT for a spin-projection-limited sensor with 10 nl measurement volume after 1 ns measurement time. The magnetometer will allow ultrafast continuous B-field measurements in many fields, including spin chemistry, spin physics, and plasma physics.

Evanescent-wave and ambient chiral sensing by signal-reversing cavity ringdown polarimetry.

Detecting and quantifying chirality is important in fields ranging from analytical and biological chemistry to pharmacology and fundamental physics: it can aid drug design and synthesis, contribute to protein structure determination, and help detect parity violation of the weak force. Recent developments employ microwaves, femtosecond pulses, superchiral light or photoionization to determine chirality, yet the most widely used methods remain the traditional methods of measuring circular dichroism and optical rotation. However, these signals are typically very weak against larger time-dependent backgrounds. Cavity-enhanced optical methods can be used to amplify weak signals by passing them repeatedly through an optical cavity, and two-mirror cavities achieving up to 10(5) cavity passes have enabled absorption and birefringence measurements with record sensitivities. But chiral signals cancel when passing back and forth through a cavity, while the ubiquitous spurious linear birefringence background is enhanced. Even when intracavity optics overcome these problems, absolute chirality measurements remain difficult and sometimes impossible. Here we use a pulsed-laser bowtie cavity ringdown polarimeter with counter-propagating beams to enhance chiral signals by a factor equal to the number of cavity passes (typically >10(3)); to suppress the effects of linear birefringence by means of a large induced intracavity Faraday rotation; and to effect rapid signal reversals by reversing the Faraday rotation and subtracting signals from the counter-propagating beams. These features allow absolute chiral signal measurements in environments where background subtraction is not feasible: we determine optical rotation from α-pinene vapour in open air, and from maltodextrin and fructose solutions in the evanescent wave produced by total internal reflection at a prism surface. The limits of the present polarimeter, when using a continuous-wave laser locked to a stable, high-finesse cavity, should match the sensitivity of linear birefringence measurements (3 × 10(-13) radians), which is several orders of magnitude more sensitive than current chiral detection limits and is expected to transform chiral sensing in many fields.

Photofragment spin-polarization measurements via magnetization quantum beats: dynamics of DI photodissociation.

We report the electron-spin polarization of D atoms from the photodissociation of DI, at 213 nm and 266 nm, by measuring the magnetization quantum beats of the D atoms with a pick-up coil. We determine that the polarization P is large at both wavelengths (|P|∼ 1), however it is positive at 213 nm, and negative at 266 nm. These results, in both cases, are of opposite sign to calculations, which assume adiabatic dissociation along the A1Π1 or a3Π1 states. We interpret these results as evidence that nonadiabatic coupling between these states needs to be included for the theoretical treatment of DI photodissociation.

Spin-Polarized Hydrogen Depolarization Rates at High Hydrogen Halide Pressures: Hyperfine Depolarization via the HY-H Complex.

We measure the magnetization quantum beats of spin-polarized hydrogen (SPH) and spin-polarized deuterium (SPD) with a pickup coil, from the UV photodissociation of HCl, HBr, and DI, in the 5-5000 mbar pressure range. The pressure-dependent depolarization rate is linear at low pressures and reaches a plateau at higher pressures. The high-pressure depolarization rate is observed to be proportional to the halogen nuclear electric quadrupole coupling constant. We also investigate how the presence of an inert gas, SF6 or N2, affects the depolarization rate. The results are explained using a model in which depolarization occurs predominantly through an HY-H intermediate species (Y = Cl, Br, I).

Ultrahigh-Density Spin-Polarized H and D Observed via Magnetization Quantum Beats.

We measure nuclear and electron spin-polarized H and D densities of at least 10^{19} cm^{-3} with ∼10 ns lifetimes, from the photodissociation of HBr and DI with circularly polarized UV light pulses. This density is ∼6 orders of magnitude higher than that produced by conventional continuous-production methods and, surprisingly, at least 100 times higher than expected densities for this photodissociation method. We observe the hyperfine quantum beating of the H and D magnetization with a pickup coil, i.e., the respective 0.7 and 3 ns periodic transfer of polarization from the electrons to the nuclei and back. The 10^{19} cm^{-3} spin-polarized H and D density is sufficient for laser-driven ion acceleration of spin-polarized electrons, protons, or deuterons, the preparation of nuclear-spin-polarized molecules, and the demonstration of spin-polarized D-T or D-^{3}He laser fusion, for which a reactivity enhancement of ∼50% is expected.

Recoil Inversion in the Photodissociation of Carbonyl Sulfide near 234 nm.

We report the observation of recoil inversion of the CO (v=0, J_{CO}=66) state in the UV dissociation of lab-frame oriented carbonyl sulfide (OCS). This state is ejected in the opposite direction with respect to all other (>30) states and in absence of any OCS rotation, thus resulting in spatial filtering of this particular high-J rovibrational state. This inversion is caused by resonances occurring in shallow local minima of the molecular potential, which bring the sulfur closer to the oxygen than the carbon atom, and is a striking example where such subtleties severely modify the photofragment trajectories. The resonant behavior is observed only in the photofragment trajectories and not in their population, showing that stereodynamic measurements from oriented molecules offer an indispensable probe for exploring energy landscapes.

Highly Nuclear-Spin-Polarized Deuterium Atoms from the UV Photodissociation of Deuterium Iodide.

We report a novel highly spin-polarized deuterium (SPD) source, via the photodissociation of deuterium iodide at 270 nm. I(^{2}P_{3/2}) photofragments are ionized with m-state selectivity, and their velocity distribution measured via velocity-map slice imaging, from which the D polarization is determined. The process produces ∼100% electronically polarized D at the time of dissociation, which is then converted to ∼60% nuclear D polarization after ∼1.6 ns. These production times for SPD allow collision-limited densities of ∼10^{18} cm^{-3} and at production rates of ∼10^{21} s^{-1} which are 10^{6} and 10^{4} times higher than conventional (Stern-Gerlach separation) methods, respectively. We discuss the production of SPD beams, and combining high-density SPD with laser fusion, to investigate polarized D-T, D-^{3}He, and D-D fusion.

Alignment of the hydrogen molecule under intense laser fields.

Alignment of the electronically excited E,F state of the H2 molecule is studied using the velocity mapping imaging technique. Photofragment images of H+ due to the dissociation mechanism that follows the 2-photon excitation into the (E,F; ν = 0, J = 0) electronic state show a strong dependence on laser intensity, which is attributed to the high polarizability anisotropy of the H2 (E,F) state. We observe a marked structure in the angular distribution, which we explain as the interference between the prepared J = 0 and Stark-mixed J = 2 rovibrational states of H2, as the laser intensity increases. Quantification of these effects allows us to extract the polarizability anisotropy of the H2 (E,F J = 0) state yielding a value of 312 ± 82 a.u. (46 Å3). By comparison, CS2 has 10 Å3, I2 has 7 Å3, and hydrochlorothiazide (C7H8ClN3O4S2) has about 25 Å3 meaning that we have created the most easily aligned molecule ever measured, by creating a mixed superposition state that is highly anisotropic in its polarizability.

Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals.

We present the theory and experimental details for chiral-cavity-ring-down polarimetry and magnetometry, based on ring cavities supporting counterpropagating laser beams. The optical-rotation symmetry is broken by the presence of both chiral and Faraday birefringence, giving rise to signal reversals which allow rapid background subtractions. We present the measurement of the specific rotation at 800 nm of vapors of α-pinene, 2-butanol, and α-phellandrene, the measurement of optical rotation of sucrose solutions in a flow cell, the measurement of the Verdet constant of fused silica, and measurements and theoretical treatment of evanescent-wave optical rotation at a prism surface. Therefore, these signal-enhancing and signal-reversing methods open the way for ultrasensitive polarimetry measurements in gases, liquids and solids, and at surfaces.

Sensitivity enhancement for evanescent-wave sensing using cavity-ring-down ellipsometry.

We demonstrate a method to increase the sensitivity of the s-p phase shift under total internal reflection (TIR) for optical sensing. This is achieved by the introduction of two simple dielectric layers to the TIR surface of a fused silica prism. The enhanced sensitivity is demonstrated using evanescent-wave cavity-ring-down-ellipsometry by measuring the refractive index of liquid mixtures and by studying the adsorption of polymers to the TIR surface of the fused silica prism.

Parent-molecule rotational depolarization of photofragment angular momentum distributions: diatomic and polyatomic molecules.

We extend the A(q)(k) polarization-parameter model, which describes product angular momentum polarization from one photon photodissociation of polyatomic molecules in the molecular frame [J. Chem. Phys., 2010, 132, 224310], to the case of rotating parent molecules. The depolarization of the A(q)(k) is described by a set of rotational depolarization factors that depend on the angle of rotation of the molecular axis γ. We evaluate these rotational depolarization factors for the case of dissociating diatomic molecules and demonstrate that they are in complete agreement with the results of Kuznetsov and Vasyutinskii [J. Chem. Phys., 2005, 123, 034307] obtained from a fully quantum mechanical approach of the same problem, showing the effective equivalence of the two approaches. We further evaluate the set of rotational depolarization factors for the case of dissociating polyatomic molecules that have three (near) equal moments of inertia, thus extending these calculations to polyatomic systems. This ideal case yields insights for the dissociation of polyatomic molecules of various symmetries when we compare the long lifetime limit with the results obtained for the diatomic case. In particular, in the long lifetime limit the depolarization factors of the A(0)(k) (odd k), Re(A(1)(k)) (even k) and Im(A(1)(k)) (odd k) for diatomic molecules vanish; in contrast, for polyatomic molecules the depolarization factors for the A(0)(k) (odd k) reduce to a value of 1/3, whereas for the Re(A(1)(k)) (even k) and Im(A(1)(k)) (odd k) they reduce to 1/5.

Towards the complete experiment: measurement of S((1)D2) polarization in correlation with single rotational states of CO(J) from the photodissociation of oriented OCS(v2 = 1|JlM = 111).

In this paper we report slice imaging polarization experiments on the state-to-state photodissociation at 42,594 cm(-1) of spatially oriented OCS(v(2) = 1|JlM = 111) → CO(J) + S((1)D(2)). Slice images were measured of the three-dimensional recoil distribution of the S((1)D(2)) photofragment for different polarization geometries of the photolysis and probe laser. The high resolution slice images show well separated velocity rings in the S((1)D(2)) velocity distribution. The velocity rings of the S((1)D(2)) photofragment correlate with individual rotational states of the CO(J) cofragment in the J(CO) = 57-65 region. The angular distribution of the S((1)D(2)) velocity rings are extracted and analyzed using two different polarization models. The first model assumes the nonaxial dynamics evolves after excitation to a single potential energy surface of an oriented OCS(v(2) = 1|JlM = 111) molecule. The second model assumes the excitation is to two potential energy surfaces, and the OCS molecule is randomly oriented. In the high J region (J(CO) = 62-65) it appears that both models fit the polarization very well, in the region J(CO) = 57-61 both models seem to fit the data less well. From the molecular frame alignment moments the m-state distribution of S((1)D(2)) is calculated as a function of the CO(J) channel. A comparison is made with the theoretical m-state distribution calculated from the long-range electrostatic dipole-dipole plus quadrupole interaction model. The S((1)D(2)) photofragment velocity distribution shows a very pronounced strong peak for S((1)D(2)) fragments born in coincidence with CO(J = 61).

Ultrahigh-density spin-polarized hydrogen isotopes from the photodissociation of hydrogen halides: new applications for laser-ion acceleration, magnetometry, and polarized nuclear fusion.

Recently, our group produced spin-polarized hydrogen (SPH) atoms at densities of at least 1019 cm-3 from the photodissociation of hydrogen halide molecules with circularly polarized UV light and measured them via magnetization-quantum beats with a pickup coil. These densities are approximately 7 orders of magnitude higher than those produced using conventional methods, opening up new fields of application, such as ultrafast magnetometry, the production of polarized MeV and GeV particle beams, such as electron beams with intensities approximately 104 higher than current sources, and the study of polarized nuclear fusion, for which the reaction cross sections of D-T and D-3He reactions are expected to increase by 50% for fully polarized nuclear spins. We review the production, detection, depolarization mechanisms, and potential applications of high-density SPH.

Photofragment angular momentum distributions in the molecular frame. III. Coherent effects in the photodissociation of polyatomic molecules with circularly polarized light.

We extend the a(q) (k)(s) polarization parameter model [T. P. Rakitzis and A. J. Alexander, J. Chem. Phys. 132, 224310 (2010)] to describe the components of the product angular momentum polarization that arise from the one-photon photodissociation of asymmetric top molecules with circularly polarized photolysis light, and provide a general equation for fitting experimental signals. We show that the only polarization parameters that depend on the helicity of the circularly polarized photolysis light are the A(0) (k) and Re[A(1) (k)] (with odd k) and the Im[A(1) (k)] (with even k); in addition, for the unique recoil destination (URD) approximation [for which the photofragment recoil v arises from a unique parent molecule geometry], we show that these parameters arise only as a result the interference between at least two dissociative electronic states. Furthermore, we show that in the breakdown of the URD approximation (for which the photofragment recoil v arises from a distribution of parent molecule geometries), these parameters can also arise for dissociation via a single dissociative electronic state. In both cases, the A(0) (k) and Re[A(1) (k)] parameters (with odd k) are proportional to cosΔφ, and the Im[A(1) (k)] parameters (with even k) are proportional to sinΔφ, where Δφ is the phase shift (or average phase shift) between the interfering paths so that Δφ can be determined directly from the A(q) (k), or from ratios of these A(q) (k) parameters. Therefore, the determination of these A(q) (k) parameters with circularly polarized photolysis light allows the unambiguous measurement of coherent effects in polyatomic-molecule photodissociation.

Photofragment angular momentum distributions in the molecular frame. II. Single state dissociation, multiple state interference, and nonaxial recoil in photodissociation of polyatomic molecules.

We present an a(q) (k)(s) polarization-parameter model to describe product angular momentum polarization from the one-photon photodissociation of polyatomic molecules in the molecular frame. We make the approximation that the final photofragment recoil direction is unique and described by the molecular frame polar coordinates (alpha,phi(i)), for which the axial recoil approximation is a special case (e.g., alpha=0). This approximation allows the separation of geometrical and dynamical factors, in particular, the expression of the experimental sensitivities to each of the a(q) (k)(s) in terms of the molecular frame polar angles (chi(i),phi(i)) of the transition dipole moment mu(i). This separation is applied to the linearly polarized photodissociation of polyatomic molecules (asymmetric, symmetric, and spherical top molecules are discussed) and to all dissociation mechanisms that satisfy our recoil approximation, including those with nonaxial recoil and multiple state interference, giving important insight into the geometrical properties of the photodissociation mechanism. For example, we demonstrate that the ratio of polarization parameters A(0) (k)(aniso)/A(0) (k)(iso)=beta (where beta is the spatial anisotropy parameter) is an indication that the dynamics can be explained by a single dissociative state. We also show that for asymmetric top photodissociation, the sensitivity to the a(1) (k)(s) parameters, which can arise either from single-surface or multiple-surface interference mechanisms, is nonzero only for components of the transition dipole moments within the v-d plane of the recoil frame.

(2+1) laser-induced fluorescence of spin-polarized hydrogen atoms.

We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments.

Cavity ring-down ellipsometry.

We demonstrate the enhancement of ellipsometric measurements by multiple reflections of a polarized light pulse on a highly reflective target surface, using an optical cavity. The principle is demonstrated by measuring the adsorbed amount of a molecular vapor (fenchone) onto the ring-cavity mirrors. A phase shift sensitivity of about 10(-2) degrees in a single laser pulse is achieved in 1 micros. Further improvements are discussed that should allow sensitivities of at least 10(-4) degrees , surpassing current commercial ellipsometers, but also surpassing their time resolution by several orders of magnitude, allowing the uses of sensitive ellipsometry to be expanded to include the study of fast surface phenomena with submicrosecond resolution.

Laser detection of spin-polarized hydrogen from HCl and HBr photodissociation: comparison of H- and halogen-atom polarizations.

Thermal HCl and HBr molecules were photodissociated using circularly polarized 193 nm light, and the speed-dependent spin polarization of the H-atom photofragments was measured using polarized fluorescence at 121.6 nm. Both polarization components, described by the a(0)(1)(perpendicular) and Re[a(1)(1)(parallel, perpendicular)] parameters which arise from incoherent and coherent dissociation mechanisms, are measured. The values of the a(0)(1)(perpendicular) parameter, for both HCl and HBr photodissociation, are within experimental error of the predictions of both ab initio calculations and of previous measurements of the polarization of the halide cofragments. The experimental and ab initio theoretical values of the Re[a(1)(1)(parallel, perpendicular)] parameter show some disagreement, suggesting that further theoretical investigations are required. Overall, good agreement occurs despite the fact that the current experiments photodissociate molecules at 295 K, whereas previous measurements were conducted at rotational temperatures of about 15 K.