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Journal of Chemical Physics / Volume 129 / Issue 12 / ARTICLES / Theoretical Methods and Algorithms

J. Chem. Phys. 129, 124102 (2008); http://dx.doi.org/10.1063/1.2977741 (8 pages)

Laser-induced nuclear magnetic resonance splitting in hydrocarbons

Suvi Ikäläinen1, Perttu Lantto2, Pekka Manninen3, and Juha Vaara1

1Laboratory of Physical Chemistry, Department of Chemistry, University of Helsinki, P.O. Box 55, A.I. Virtasen aukio 1, Helsinki FIN-00014, Finland
2NMR Research Group, Department of Physical Sciences, University of Oulu, P.O. Box 3000, Oulu FIN-90014, Finland
3Center for High-Performance Computing and Networking CSC, P.O. Box 405, FIN-02101 Espoo, Finland

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(Received 10 June 2008; accepted 11 August 2008; published online 22 September 2008)

Irradiation of matter with circularly polarized light (CPL) shifts all nuclear magnetic resonance (NMR) lines. The phenomenon arises from the second-order interaction of the electron cloud with the optical field, combined with the orbital hyperfine interaction. The shift occurs in opposite directions for right and left CPL, and rapid switching between them will split the resonance lines into two. We present ab initio and density functional theory predictions of laser-induced NMR splittings for hydrocarbon systems with different sizes: ethene, benzene, coronene, fullerene, and circumcoronene. Due to the computationally challenging nature of the effect, traditional basis sets could not be used for the larger systems. A novel method for generating basis sets, mathematical completeness optimization, was employed. As expected, the magnitude of the spectral splitting increases with the laser beam frequency and polarizability of the system. Massive amplification of the effect is also observed close to the optical excitation energies. A much larger laser-induced splitting is found for the largest of the present molecules than for the previously investigated noble gas atoms or small molecules. The laser intensity required for experimental detection of the effect is discussed.

© 2008 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. THEORY
    1. Laser-induced splitting
    2. Completeness-optimized basis sets
  3. CALCULATIONS
  4. RESULTS AND DISCUSSION
    1. Basis-set convergence
    2. Standard laser frequencies
    3. Behavior near optical resonance frequencies
    4. Experimental detection
  5. CONCLUSIONS

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KEYWORDS and PACS

Keywords

ab initio calculations, density functional theory, hyperfine interactions, nuclear magnetic resonance, organic compounds, spectral line shift

PACS

  • 33.25.+k

    Nuclear resonance and relaxation

  • 33.70.Jg

    Line and band widths, shapes, and shifts

  • 33.15.Pw

    Fine and hyperfine structure

  • 31.15.aj

    Relativistic corrections, spin-orbit effects, fine structure; hyperfine structure

  • 31.15.es

    Applications of density-functional theory (e.g., to electronic structure and stability; defect formation; dielectric properties, susceptibilities; viscoelastic coefficients; Rydberg transition frequencies)

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.2977741

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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