CaltechAUTHORS
  A Caltech Library Service

Theory of selective excitation of multiple-quantum transitions

Warren, W. S. and Weitekamp, D. P. and Pines, A. (1980) Theory of selective excitation of multiple-quantum transitions. Journal of Chemical Physics, 73 (5). pp. 2084-2099. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:WARjcp80

[img]
Preview
PDF
See Usage Policy.

1406Kb

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:WARjcp80

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 2pi/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.


Item Type:Article
Additional Information:Copyright © 1980 American Institute of Physics. (Received 18 April 1980; accepted 12 May 1980) We wish to thank Gary Drobny, Dr. Luciano Mueller, James Murdoch, Steve Sinton, and Jau Tang for stimulating discussions, and Terry Judson for her patience in typing the manuscript. W.S.W. holds a National Science Foundation Graduate Fellowship. This research was supported by the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy under contract no. W-7405-Eng-48.
Subject Keywords:ENERGY–LEVEL TRANSITIONS, EXCITATION, ABSORPTION SPECTRA, NMR SPECTRA, ZEEMAN EFFECT
Record Number:CaltechAUTHORS:WARjcp80
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:WARjcp80
Alternative URL:http://dx.doi.org/10.1063/1.440403
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10867
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:14 Jun 2008
Last Modified:26 Dec 2012 10:05

Repository Staff Only: item control page