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Accurate determination of molecular structure and vibrational force constants by computation


Characterization of the crystal forces that alter the geometry and vibrations of a molecule when it goes from the free to the solid state requires a comparison of the relevant properties between gas phase studies (usually electron diffraction, microwave spectroscopy, orab initio computation) and solid state experiments (usually x-ray or neutron diffraction). The present state ofab initio computation is reviewed with emphasis on the requirement for high accuracy and reliability, so that small alterations in the crystal can be detected, and on the desirability of carrying out the computations on as large systems as possible.

A distinction is made between the determination of relative values with high precision so that trends in structure or vibrational frequencies can be followed and the determination of absolute values to permit intercomparison between different techniques. In both cases, present limitations are discussed along with a few newer ideas for extending those limits in the direction of larger systems without loss of accuracy.

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Paper from Conference on Quantum Theory and Experiment, July 1986

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Boggs, J.E. Accurate determination of molecular structure and vibrational force constants by computation. Phys Chem Minerals 14, 407–412 (1987).

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  • Microwave
  • Solid State
  • Mineral Resource
  • Electron Diffraction
  • State Experiment