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Journal of Modern Optics

Sharpening accepted thermodynamic wisdom via quantum control: or cooling to an internal temperature of zero by external coherent control fields without spontaneous emission

Marlan O. Scully, Yakir Aharonov, Kishore T. Kapale, David J. Tannor, Georg Süssmann, HERBERT WALTHER

Published Nov 1, 2002• 5 citations
Publisher

Abstract

Cooling of internal atomic and molecular states via optical pumping and laser cooling of the atomic velocity distribution, rely on spontaneous emission. The outstanding success of such examples, taken together with general arguments, has led to the widely held notion that radiative cooling requires spontaneous emission. We here show by specific examples and direct calculation, based primarily on breaking emission-absorption symmetry as in lasing without inversion, that cooling of internal states by external coherent control fields is possible. We also show that such coherent schemes allow us to practically reach absolute zero in a finite number of steps, in contrast to some statements of the third law of thermodynamics.

DOI
10.1080/0950034021000011392

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Cooling of internal atomic and molecular states via optical pumping and laser cooling of the atomic velocity distribution, rely on spontaneous emission. The outstanding success of such examples, taken together with general arguments, has led to the widely held notion that radiative cooling requires spontaneous emission. We here show by specific examples and direct calculation, based primarily on breaking emission-absorption symmetry as in lasing without inversion, that cooling of internal states by external coherent control fields is possible. We also show that such coherent schemes allow us to practically reach absolute zero in a finite number of steps, in contrast to some statements of the third law of thermodynamics.
In the last several years we have discovered a variety of remarkable pulse strategies for manipulating molecular motion by employing a design strategy we call “local optimization.'' Here we review the concept of local optimization and contrast it with optimal control theory. By way of background, we give highlights from two recent examples of the method: (1) a strategy for eliminating population transfer to one or many excited electronic states during strong field excitation, an effect we call ‘optical paralysis’; (2) a generalization of the counterintuitive STIRAP (stimulated Raman adiabatic passage) pulse sequence from three levels to N levels, a strategy we call ‘straddling STIRAP.' We then turn to a third example, which is the main subject of this paper: laser cooling of molecular internal degrees of freedom. We study a model that includes both coherent interaction with the radiation field and spontaneous emission; the latter is necessary to carry away the entropy from the molecule. An optimal control calculation was performed first and succeeded in producing vibrational cooling, but the resulting pulse sequence was difficult to interpret. Local optimization subsequently revealed the cooling mechanism: the instantaneous phase of the laser is locked to the phase of the transition dipole moment between the excited state amplitude and v=0 of the ground state. Thus, the molecules that reach v=0 by spontaneous emission become decoupled from the field, and no longer absorb, while molecules in all other states are continually repumped. The mechanism could be called “vibrationally selective coherent population trapping,'' in analogy to the corresponding mechanism of velocity selective coherent population trapping in atoms for sub-Doppler cooling of translations.
The usual form of electromagnetic forces is given by but for neutral atoms q = 0. The next order of force is the dipole term, but this also vanishes because neutral atoms have no inherent dipole moment. However, a dipole moment can be induced by a field, and this is most efficient if the field is alternating near the atomic resonance frequency. Since these frequencies are typically in the optical range, dipole moments are efficiently induced by shining nearly resonant light on the atoms. Laser cooling and trapping rely on the interaction between laser light and atoms to exert a controllable force on the atoms, and many sophisticated schemes have been developed using the special properties of the interaction. This chapter begins with the simplest schemes for exerting optical forces on atoms, namely a single-frequency light field interacting with a two-level atom. Although this is the simplest possible scheme, it is pedagogically valuable because it shows many of the features that will be encountered further on. The ultimate temperature using such a scheme is limited, but lower temperatures can be achieved with multilevel atoms. This topic is addressed later in the chapter. Two kinds of optical forces When an atom absorbs nearly resonant light, it makes a transition to the excited state, and its subsequent return to the ground state can be either by spontaneous or by stimulated emission. The nature of the optical force that arises from these two different processes is quite different, and will be described separately [1]. The spontaneous emission case is different from the familiar quantum mechanical calculations using state vectors to describe the state of the system, because spontaneous emission causes the state of the system to evolve from a pure state into a mixed state (see Exercise 6.9). Spontaneous emission is an essential ingredient for the dissipative nature of the optical forces in monochromatic light, and the density matrix is needed to describe it (see Chap. 6). When an atom absorbs light, its energy excites the atom and its angular momentum changes the electron's orbit. Both of these are internal atomic properties. However, the linear momentum of the light, can change only the external, translational motion of the atom.
The quantum-mechanical and thermodynamic properties of a three-level molecular cooling cycle are derived. An inadequacy of earlier models is rectified in accounting for the spontaneous emission and absorption associated with the coupling to the coherent driving field via an environmental reservoir. This additional coupling need not be dissipative, and can provide a thermal driving force-the quantum analog of classical absorption chillers. The dependence of the maximum attainable cooling rate on temperature, at ultralow temperatures, is determined and shown to respect the recently established fundamental bound based on the second and third laws of thermodynamics.
Optimal control theory is applied to laser cooling of molecules. The objective is to cool vibrations, using shaped pulses synchronized with the spontaneous emission. The optimal mechanism is found to operate by a “vibrationally selective coherent population trapping”. The trapping condition is that the instantaneous phase of the laser is locked to the phase of the transition dipole moment of v=0 with the excited population. The molecules that reach v=0 by spontaneous emission are then trapped, while the others are continually repumped.
A laser-cooling scheme for molecules is presented based on repeated cycle of zero-velocity selection, deceleration, and irreversible accumulation. Although this scheme also employs a single spontaneous emission as in [Raymond Ooi, Marzlin, and Audretsch, Eur. Phys. J. D 22, 259 (2003)], in order to circumvent the difficulty of maintaining closed pumping cycles in molecules, there are two distinct features which make the cooling process of this scheme faster and more practical. First, the zero-velocity selection creates a narrow velocity-width population with zero mean velocity, such that no further deceleration (with many stimulated Raman adiabatic passage (STIRAP) pulses) is required. Second, only two STIRAP processes are required to decelerate the remaining hot molecular ensemble to create a finite population around zero velocity for the next cycle. We present a setup to realize the cooling process in one dimension with trapping in the other two dimensions using a Stark barrel. Numerical estimates of the cooling parameters and simulations with density matrix equations using OH molecules show the applicability of the cooling scheme. For a gas at temperature T=1T=1T=1 K, the estimated cooling time is only 222 ms, with phase-space density increased by about 30 times. The possibility of extension to three-dimensional cooling via thermalization is also discussed.