Finesse and sensitivity gain in cavity-enhanced absorption spectroscopy of biomolecules in solution

We describe a ‘wet mirror’ apparatus for cw cavity-enhanced absorption measurements with Bacteriochlorophyll a (BChla) in solution and show that it achieves the full sensitivity gain (≈ 2.3×10^4) afforded by the finesse (3.4 × 10^4) and loss distribution of our optical resonator. This result provides an important proof-of-principle demonstration for solution-phase cavity-enhanced spectroscopy; straightforward extrapolation to a system with state-of-the-art low-loss mirrors and shot-noise-limited performance indicates that single molecule sensitivity in liquids is within reach of current technology. With the probe laser locked to the cavity resonance, our instrument achieves a sensitivity ≈3.4×10^−8/√Hz (for a sample of length 1.75 mm) with 100 kHz bandwidth and can reliably detect sub-nM concentrations of BChla with 1 ms integration time

A sub-Doppler resolution double resonance molecular beam infrared spectrometer operating at chemically relevant energies (~2 eV)

A molecular beam spectrometer capable of achieving sub-Doppler resolution at 2 eV (~18 000 cm^–1) of vibrational excitation is described and its performance demonstrated using the CH stretch chromophore of HCN. Two high finesse resonant power-buildup cavities are used to excite the molecules using a sequential double resonance technique. A v = 0-->2 transition is first saturated using a 1.5 µm color center laser, whereupon a fraction of the molecules is further excited to the v = 6 level using an amplitude modulated Ti:Al2O3 laser. The energy absorbed by the molecules is detected downstream of both excitation points by a cryogenically cooled bolometer using phase sensitive detection. A resolution of approximately 15 MHz (i.e., three parts in 10^8) is demonstrated by recording a rotational line in the v = 6 manifold of HCN. Scan speeds of up to several cm^–1/h were obtained, with signal-to-noise ratios in excess of 100. The high signal-to-noise ratio and a dynamic range of 6×10^4 means that future experiments to study statistical intramolecular vibrational energy redistribution in small molecules and unimolecular isomerizations can be attempted. We would also like to point out that, with improved metrology in laser wavelengths, this instrument can also be used to provide improved secondary frequency standards based upon the rovibrational spectra of molecules

Rotation in liquid 4^4He: Lessons from a toy model

This paper presents an analysis of a model problem, consisting of two interacting rigid rings, for the rotation of molecules in liquid $^4$He. Due to Bose symmetry, the excitation of the rotor corresponding to a ring of N helium atoms is restricted to states with integer multiples of N quanta of angular momentum. This minimal model shares many of the same features of the rotational spectra that have been observed for molecules in nanodroplets of $\approx 10^3 - 10^4$ helium atoms. In particular, this model predicts, for the first time, the very large enhancement of the centrifugal distortion constants that have been observed experimentally. It also illustrates the different effects of increasing rotational velocity by increases in angular momentum quantum number or by increasing the rotational constant of the molecular rotor. It is found that fixed node, diffusion Monte Carlo and a hydrodynamic model provide upper and lower bounds on the size of the effective rotational constant of the molecular rotor when coupled to the helium

A superfluid hydrodynamic model for the enhanced moments of inertia of molecules in liquid 4He

We present a superfluid hydrodynamic model for the increase in moment of inertia, $\Delta I$, of molecules rotating in liquid $^4$He. The static inhomogeneous He density around each molecule (calculated using the Orsay-Paris liquid $^4$He density functional) is assumed to adiabatically follow the rotation of the molecule. We find that the $\Delta I$ values created by the viscousless and irrotational flow are in good agreement with the observed increases for several molecules [ OCS, (HCN)$_2$, HCCCN, and HCCCH$_3$ ]. For HCN and HCCH, our model substantially overestimates $\Delta I$. This is likely to result from a (partial) breakdown of the adiabatic following approximation.Comment: 4 pages, 1 eps figure, corrected version of published paper. Erratum has been submitted for change

Importance des moments dipolaires diagonaux et non-diagonaux dans le processus de photodissociation de HCl⁺ par laser intense

Le but premier de ce projet de recherche était de modéliser le plus exactement possible le phénomène de dissociation multiphotonique de l'ion moléculaire HCl⁺. Motivé, au départ, par l'impossibilité d'obtenir expérimentalement des informations concernant la dynamique de photodissociation, le projet se transforma rapidement en une étude systématique des effets des moments dipolaires diagonaux et non-diagonaux des molécules diatomiques hétéronucléaires. La première partie de ce travail consistait en la dérivation d'une expression mathématique qui aura servi à modéliser le moment dipolaire permanent de HCl⁺, pour toutes les valeurs de distances internucléaires possibles et pour tous les états de symétrie ²II dont la courbe de potentiel est connue. Pour compléter l'étude théorique du modèle, la formulation analytique des potentiels moléculaires habillés par le champ laser a été dérivée. Cette formulation sera utilisé lors de travaux futurs concernant les effets de résonance dans les processus de photodissociation multiphotonique. Dans le but de remédier au manque de données spectroscopiques expérimentales (énergie cinétique des produits de dissociation), les simulations dépendantes du temps auront permis d'étudier le comportement de l'ion moléculaire dans les différents canaux de dissociation, indépendamment les uns des autres. Une étude exhaustive des spectres d'énergie cinétique de plus de 250 simulations n'étant pas réaliste, seuls les cas limites seront discutés et une analyse qualitative du phénomène de dissociation multiphotonique sera présentée. Une comparaison à d'autres méthodes de simulation complétera l'étude

Energetics and Possible Formation and Decay Mechanisms of Vortices in Helium Nanodroplets

The energy and angular momentum of both straight and curved vortex states of a helium nanodroplet are examined as a function of droplet size. For droplets in the size range of many experiments, it is found that during the pickup of heavy solutes, a significant fraction of events deposit sufficient energy and angular momentum to form a straight vortex line. Curved vortex lines exist down to nearly zero angular momentum and energy, and thus could in principle form in almost any collision. Further, the coalescence of smaller droplets during the cooling by expansion could also deposit sufficient angular momentum to form vortex lines. Despite their high energy, most vortices are predicted to be stable at the final temperature (0.38 K) of helium nanodroplets due to lack of decay channels that conserve both energy and angular momentum.Comment: 10 pages, 8 figures, RevTex 4, submitted to Phys. Rev.

A quantitative theory-versus-experiment comparison for the intense laser dissociation of H2+

A detailed theory-versus-experiment comparison is worked out for H$_2^+$ intense laser dissociation, based on angularly resolved photodissociation spectra recently recorded in H.Figger's group. As opposite to other experimental setups, it is an electric discharge (and not an optical excitation) that prepares the molecular ion, with the advantage for the theoretical approach, to neglect without lost of accuracy, the otherwise important ionization-dissociation competition. Abel transformation relates the dissociation probability starting from a single ro-vibrational state, to the probability of observing a hydrogen atom at a given pixel of the detector plate. Some statistics on initial ro-vibrational distributions, together with a spatial averaging over laser focus area, lead to photofragments kinetic spectra, with well separated peaks attributed to single vibrational levels. An excellent theory-versus-experiment agreement is reached not only for the kinetic spectra, but also for the angular distributions of fragments originating from two different vibrational levels resulting into more or less alignment. Some characteristic features can be interpreted in terms of basic mechanisms such as bond softening or vibrational trapping.Comment: submitted to PRA on 21.05.200

Helium nanodroplet isolation ro-vibrational spectroscopy: methods and recent results

In this article, recent developments in HElium NanoDroplet Isolation (HENDI) spectroscopy are reviewed, with an emphasis on the infrared region of the spectrum. Topics discussed include experimental details, comparison of radiation sources, symmetry issues of the helium solvation structure, sources of line broadening, changes in spectroscopic constants upon solvation, and applications including formation of novel chemical structures.Comment: 24 pages, 8 figures, 3 tables; to be published in the Journal of Chemical Physic