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The Journal of Chemical Physics

Theory of selective excitation of multiple-quantum transitions

W. S. Warren, D. P. Weitekamp, Alexander Pines

Published Sep 1, 1980• 193 citations
Publisher

Abstract

The question of whether a molecule can be made to absorb and emit photons only in groups of n is treated. Pulse sequences are introduced which in effect selectively induce the absorption of only groups of n photons. This causes only n-quantum transitions even when many other transitions might be resonant. The technique involves repeated phase shifts of 2π/n in the radiation to build up the selected coherences and cancel all other coherences, and is applicable to a wide range of spectroscopic systems. Coherent averaging theory is extended to describe selective sequences and demonstrates that n-quantum selectivity is possible to arbitrarily high order in the average Hamiltonian expansion. High-order selectivity requires many phase shifts, however, and for this reason the residual nonselective effects of sequences which are selective to only a finite order are calculated. Selective sequences are applied to the multiple-quantum NMR of oriented molecules, where in combination with time reversal sequences they produce a much more efficient transfer of the population differences into selected coherences than is obtainable by normal wideband pumping. For example, the 10-quantum transition in a 10-spin system can be enhanced by more than four orders of magnitude. Experiments on selective excitaiton of the 4-quantum transitions in oriented benzene verify the expected enhancement.

DOI
10.1063/1.440403

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The question of whether a molecule can be made to absorb and emit photons only in groups of n is treated. Pulse sequences are introduced which in effect selectively induce the absorption of only groups of n photons. This causes only n-quantum transitions even when many other transitions might be resonant. The technique involves repeated phase shifts of 2π/n in the radiation to build up the selected coherences and cancel all other coherences, and is applicable to a wide range of spectroscopic systems. Coherent averaging theory is extended to describe selective sequences and demonstrates that n-quantum selectivity is possible to arbitrarily high order in the average Hamiltonian expansion. High-order selectivity requires many phase shifts, however, and for this reason the residual nonselective effects of sequences which are selective to only a finite order are calculated. Selective sequences are applied to the multiple-quantum NMR of oriented molecules, where in combination with time reversal sequences they produce a much more efficient transfer of the population differences into selected coherences than is obtainable by normal wideband pumping. For example, the 10-quantum transition in a 10-spin system can be enhanced by more than four orders of magnitude. Experiments on selective excitaiton of the 4-quantum transitions in oriented benzene verify the expected enhancement.
In this paper we present novel and simple pulse sequences for enhancing the intensity of forbidden or highly nonresonant optical transitions. These sequences provide a straightforward approach to circumventing the most serious limitation of optical coherent transient spectroscopy: Available laser intensities are often insufficient to excite a significant fraction of the ground state population into desired excited states, either because of large inhomogeneous broadening or, in the case of multiphoton absorption, large anharmonicities. Optical phase modulation (which can be produced by an acousto-optic modulator) or amplitude modulation (which can be produced by an interferometer) with carefully chosen pulse flip angles and delays can effectively remove even very large energy mismatches, thus permitting essentially complete population inversions arbitrarily far from resonance. Coherent averaging theory and computer calculations are used to derive particularly valuable sequences. Pumping enhancement of 103–105 (depending on individual molecular parameters) for these modulated pulse sequences are predicted. Specific applications to multiphoton pumping of local vibrational modes are discussed.
A general theory has been developed to calculate the response, in NMR conditions, of a spin system irradiated by two nearly resonant waves having different frequencies and intense enough to produce an appreciable saturation. The absorption signal has been calculated employing the statistical operator technique, treating the electromagnetic field by the second quantization formalism. Two kinds of transitions are expected: The first one arises from processes in which n photons of one wave are emitted and n photons of the other wave are absorbed, the second one arises from processes involving the emission of n photons of one wave and the absorption of n ± 1 photons of the other. In the first case all the transitions coalesce in a single dispersionlike signal, which occurs when the frequencies of the two waves are nearly the same; in the second case a many-line spectrum occurs in which emission and absorption lines are present. The experimental results here reported strictly agree with theoretical previsions.
Two different approaches to multiphoton excitation of an anharmonic multilevel system are presented. Both methods result in nearly complete population of the upper state. The first approach involving phase shifting portions of the coherent excitation is treated analytically with square pulses. The second approach uses sequences of several pulses with selected relative phase and delays. Some numerical examples are presented for three- and four-photon excitation of the vibrational level structure of CH3F. This particular molecule is again taken as model to demonstrate four-photon excitation with a five pulse sequence, taking into account the rotational line structure. The rotational line distribution in the upper state is seen to correspond to a lower temperature than in the ground state.
Residual dipolar couplings can be used to increase the number of qubits for quantum information processing. We have used molecules containing 3, 5 and 8 spins oriented in a liquid crystal matrix, and exploited the residual dipolar coupling to demonstrate quantum information processing in them. Transition assignment is performed using HET-Z-COSY experiment and qubit addressability is achieved by transition selective pulses. It is expected that using this protocol higher qubits can be achieved. For the implementations reported in this work, evolution under the internal Hamiltonian was not explored. It is however interesting to investigate how effectively the evolution under internal Hamiltonian can be manipulated to implement quantum algorithms in these systems. Recently an approach has been reported in this direction, where a new method of preparing pseudopure states in oriented systems by exciting selected multiple quantum using evolution under effective dipolar Hamiltonian, has been demonstrated [24].
The coherent control of atomic energy level population is important for several areas physics and engineering including fluorescent spectroscopy, resonantly enhanced multiphoton ionization, harmonic generation, remote sensing and lasing. At low intensities where the Stark shift can be neglected, coherent control mechanisms usually exploit resonances created from stationary energy states dressed by integer multiples of the photon energy. However, in the strong field limit where large laser pulse intensities lead to significant Stark shifts, the resonant conditions are dynamic both in time and space and will likely not be satisfied for the entire laser pulse or beam.\n\nIn this research, we experimentally and theoretically demonstrate coherent control of atomic energy level population in sodium vapor as well as the selective excitation of sodium Rydberg levels using high intensity laser pulses. We also make a direct measurement of the ponderomotive shift of the continuum. While techniques based on resonance interferences and rapid adiabatic passage have been introduced for selective excitation, the conditions that must be satisfied for these phenomena can be hampered by short femtosecond pulse durations and large Stark shifts. In contrast, a technique referred to here as Resonance Sampling, uses the AC Stark shifts to selectively induce Freeman resonances and is resilient to changes in the spectral phase. Freeman resonances established in this way can result in population inversion of the excited state, and may lead to new lasing mediums and remote sensing applications.\n\n\nIn this research, we experimentally and theoretically demonstrate coherent control of atomic energy level population in sodium vapor as well as the selective excitation of sodium Rydberg levels using high intensity laser pulses. While techniques based on resonance interferences and rapid adiabatic passage have been introduced for selective excitation, the conditions that must be satisfied for these phenomena can be hampered by short femtosecond pulse durations and large Stark shifts. In contrast, a technique referred to here as Resonance Sampling, uses the AC Stark shifts to selectively induce Freeman resonances and is resilient to changes in the spectral phase. Freeman resonances established in this way can result in population inversion of the excited state, and may lead to new lasing mediums and remote sensing applications.
Experiments in coherent spectroscopy correspond to control of quantum-mechanical ensembles guiding them from initial to final target states. The control inputs (pulse sequences) that accomplish these transfers should be designed to minimize the effects of relaxation and to optimize the sensitivity of the experiments. For example in Nuclear Magnetic Resonance (NMR) spectroscopy, a question of fundamental importance is what is the maximum efficiency of polarization or coherence transfer between coupled spins in the presence of relaxation. Furthermore, what is the optimal pulse sequence which achieves this efficiency? This letter is a continuation of our previous work on the above problems. Here, we attempt to answer these questions for an Ising spin chain, under the presence of transverse relaxation. The methods presented in this paper are expected to find applications not only in coherent spectroscopy but also in quantum information processing.