A closed solution to the Baker-Campbell-Hausdorff problem is described. The solution, which is based on the Cayley-Hamilton theorem, allows the entanglement between exponential operators to be described by an exact finite series expansion. Addressing specifically the special unitary Lie groups SU(2), SU(3), and SU(4), we derive expansion formulas for the entangled exponential operator as well as for the effective Hamiltonian describing the net evolution of the quantum system. The capability of our so-called exact effective Hamiltonian theory for analytical and numerical analysis is demonstrated by evaluation of multiple-pulse methods within liquid- and solid-state nuclear-magnetic-resonance spectroscopy. The examples include composite pulses for inversion, decoupling, and dipolar recoupling, as well as coherence-order- and spin-state-selective double- to single-quantum conversion, homonuclear dipolar decoupling, finite rf excitation for quadrupolar nuclei, heteronuclear coherence transfer, and gates for quantum computation.

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We present coherence-order-and spin-state-selective (COS 3 ) HSQC pulse sequences for 2(I 1zThe sequences provide the theoretical maximum transfer efficiency and improved effective resolution in the I-spin dimension and allow for heteronuclear gradient echoes without loss in sensitivity. For the antiphase transfer the sensitivity is improved by 41% relative to the previous spin-state-selective R&β-HSQC experiment, while the in-phase sequence is the first of its kind. In the regime of well-separated J doublet lines, the sensitivity enhancement amounts to 100% and 65% relative to previous antiphase and in-phase coherence-order-selective experiments, respectively. The new COS 3 HSQC experiments and previous methods are compared experimentally using β-O-methyl maltoside.

Our recent exact effective Hamiltonian theory (EEHT) for exact analysis of nuclear magnetic resonance (NMR) experiments relied on a novel entanglement of unitary exponential operators via finite expansion of the logarithmic mapping function. In the present study, we introduce simple alternant quotient expressions for the coefficients of the polynomial matrix expansion of these entangled operators. These expressions facilitate an extension of our previous closed solution to the Baker-Campbell-Hausdorff problem for SU(N) systems from N< or =4 to any N, and thereby the potential application of EEHT to more complex NMR spin systems. Similarity matrix transformations of the EEHT expansion are used to develop alternant quotient expressions, which are fully general and prove useful for evaluation of any smooth matrix function. The general applicability of these expressions is demonstrated by several examples with relevance for NMR spectroscopy. The specific form of the alternant quotients is also used to demonstrate the fundamentally important equivalence of Sylvester's theorem (also known as the spectral theorem) and the EEHT expansion.

We report analytical solutions to the unitary bound problem for coherence/polarization transfer in IS two-spin-12 systems by means of unitary operations. Theoretical upper bounds for the transfer efficiency along with the associated optimum transformation operators are obtained analytically by decomposing the unitary operator as a product of exponentials in the special unitary Lie group SU(4). Addressing NMR spectroscopy as a specific example, the method is demonstrated for the non-Hermitian transfers I−→S− and 2I−Sz→S− being relevant for heteronuclear single-quantum coherence (HSQC) experiments as well as the double- to single-quantum transfer I−S−→I−Sβ+IβS− being representative for coherence-order and spin-state-selective transfer in INADEQUATE CR experiments. Furthermore, using a Lagrangian function approach it is demonstrated how the method enables analytical description of two-dimensional bounds for Iz→Sz cross polarization.