By means of a time-resolved microwave spectroscopy experiment using the Stark switching technique, the authors have pointed out an exchange of rotational coherence from a level pair (a-a') of an A molecule to a level pair (b-b') of a B molecule in a gas at low pressure. The experiment exploits the linear Stark effect of the (a-a') line, the frequency of which is successively switched on resonance with the applied CW field to bring a coherence on the (a-a') level pair or with the (b-b') line frequency which is Stark insensitive and always off resonance with the applied CW field. The coherence exchange efficiency is maximum when the two line frequencies (a-a') and (b-b') are switched in exact resonance during a time around the transverse relaxation time T2. The radiation trapping effects are calculated and explain fairly well the experimental results obtained in a long cell. The collisional effects are shown to give a contribution which differs from the previous one only by its phase and its cell-length dependence. An experiment in a short cell is exploited to give a tentative upper limit for the collisional coherence transfers.
Considers the transfer of optical coherence from one level pair to another. The effect is isolated from the general collision expression derived by Berman (1976) and it is argued that it is best observed in transient measurements. The free decay of a four-level system is solved analytically and two regimes are found: one with oscillations displaying a beat and another with two decay rates. At the border the exponential dependence is modified. The implications for free induction decay and echo experiments are presented. Both phenomena can be used to detect the collisional transfer of coherence, and some experimental aspects of their observation are discussed.
Collision-induced coherence transfer between infrared molecular transitions is studied using a technique that permits the complete distribution of accompanying velocity changes to be determined in a simple way. The experiments are carried out by measuring the intensity of two pulse photon echoes as a function of applied Stark field at fixed large echo time delay. The velocity change distribution for coherence-transfer collisions is obtained directly as the shape of the echo intensity versus Stark field curve. Previously unpublished data for dipole-quadrupole and van der Waals interactions are presented, and a theory of coherence-transfer velocity-changing kernels is developed that is in good agreement with the data.
It has been shown recently that molecular gas samples excited with coherent light can display a variety of transient phenomena, similar to those found in nuclear magnetic resonance. This article elucidates how these coherence effects can be used to isolate or unfold molecular collision mechanisms that normally remain hidden within the optical line shape. Elastic collisions, for example, are easily detected here in two-pulse photon echo experiments for a
13CH3F vibration-rotation transition. The echo-decay function which provides a signature for the velocity-changing collision diffusion mechanism, is not just a simple exponential in time but exhibits an $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ contribution for short times and an $\mathrm{exp}(\ensuremath{-}\ensuremath{\Gamma}t)$ decay for long times. This behavior, which is unknown heretofore, contrasts with spin echoes in molecular liquids where Brownian motion leads only to the cubic decay law. An $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ behavior can be understood in terms of a solution of the Fokker-Planck equation which describes the effect of Brownian motion on echo decay. Such a treatment is valid for small phase excursions; in the case of a gas, this implies the Doppler phase factor $k\ensuremath{\Delta}u\ensuremath{\tau}\ensuremath{\ll}1$, where $\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}$ is the propagation vector of light, $\ensuremath{\Delta}u$ is a characteristic velocity jump for a binary collision, and $\ensuremath{\tau}$ is the echo-pulse delay time. When $k\ensuremath{\Delta}u\ensuremath{\tau}\ensuremath{\gg}1$ as in the long-time regime, the Fokker-Planck solution fails. We, therefore, present a new solution to the Boltzmann transport equation using a weak collision model and find agreement with the entire echo time dependence observed. The echo measurements indicate very small changes in longitudinal velocity per
13CH3F-
13CH3F collision, i.e., $\ensuremath{\Delta}u=85$ cm/sec, thereby justifying the weak-collision model. The total elastic collision cross section is 430
A˚2. It follows that elastic collisions lead to velocity thermalization in a time of \ensuremath{\sim}5 sec when the
13CH3F pressure is 1 mTorr. A comparison is also made of the
13CH3F dephasing time ${\ensuremath{\tau}}_{2}$ in a coherent Raman beat decay, which is independent of velocity-changing collisions, with the longitudinal decay time
T1. Here,
T1 represents the molecule-optical interaction time, due largely to jumps in molecular rotation (
J) and orientation (
M) state, and is obtained from a delayed nutation measurement. The fact that the pressure dependent part of ${\ensuremath{\tau}}_{2}={T}_{1}$ shows that
T1 is also independent of velocity diffusion. Futhermore, when a hole is burned in the Doppler distribution, population recovery must be due to inelastic rather than elastic collisions. Optical Carr-Purcell echoes, multiple pulse echoes, provide a direct measure of the
13CH3F transverse dephasing time
T2 without the effect of elastic collisions while being sensitive to "phase interrupting collisions." Again, we find that
T2=T1 so that phase interruptions are negligible. Had such a process dominated the two-pulse echo, an $\mathrm{exp}(\ensuremath{-}\frac{t}{{T}_{2}})$ damping would have been noticed with no $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ contribution. Thus, the present study covers several new aspects of molecular collisions. It represents the first detailed examination of velocity-changing collisions by coherence methods and without the complication of Doppler broadening.
This thesis presents work towards the development of a quantum simulator based on
87Rb
133Cs molecules using a bulk sample of up to ~4000 molecules at temperatures of ~1 µK. We demonstrate coherent control over the molecules' internal state using resonant microwave fields. We test this coherence by performing high resolution Ramsey spectroscopy of the first rotational transition and observing how the contrast of the spectroscopic fringes decay. We are able to affect the coherence of the superposition using an external laser field, as the two component states have a significant differential AC Stark shift. We extend this microwave control by including an additional microwave field, demonstrating the Autler-Townes effect with hyperfine state resolution and transfer between two hyperfine states in
N=0. We study the internal structure of the molecule in the presence of external fields focussing on controlling the differential AC Stark shift between the rotational ground state and the first excited state. We investigate the effect of the off-resonant light on the internal structure in static magnetic and electric fields. In the DC electric field we use two models to describe the molecular structure, demonstrating that at modest values of the electric field the nuclear spin angular momentum is decoupled from the rotational angular momentum of the molecule, this enables us to construct a set of optimum trapping parameters for states with
MN=0. Through careful measurements of the molecular lifetime we are able to determine that molecular losses are limited by two-body collisions. By introducing a time dependent intensity modulation to our optical trap we are further able to determine that the dominant loss process in bulk samples of ultracold
87Rb
133Cs molecules is the laser excitation of collision complexes. Finally, we investigate the collisional properties of
87Rb
133Cs with
87Rb and
133Cs atoms. We find that the loss is caused by single molecule-single atom collisions and sub-universal over a wide range of magnetic fields.
Microwave-assisted resonant collisional energy transfer process $\mathrm{Na}(\mathrm{ns})+\mathrm{Na}(\mathrm{ns})+h\ensuremath{\nu}\ensuremath{\rightarrow}\mathrm{Na}(\mathrm{np})+\mathrm{Na}((n\ensuremath{-}1)p)$ is observed between two colliding
Na(ns) atoms. The collisional resonance occurs when the microwave frequency $\ensuremath{\nu}$ equals the collisional energy defect $\frac{\ensuremath{\Delta}W}{h}$. The observed cross sections are very large (\ensuremath{\sim}
108 A˚2) and require very low microwave power, \ensuremath{\sim}10 W/
cm2. These observations are in good agreement with an intuitive two-photon absorption model for these collisions.