On QM/MM and MO/MO cluster calculations of all-atom anisotropic displacement parameters for molecules in crystal structures

The practical aspects of ab initio calculation of anisotropic displacement parameters (ADPs) for molecules in crystal structures are investigated. Computationally efficient approaches to calculate ADPs are QM/MM or MO/MO methods, where quantum chemical calculations are split into a high-level and a low-level part. Such calculations allow geometry optimizations and subsequent frequency calculations of a central molecule in a cluster of surrounding molecules as found in the crystal lattice. The frequencies and associated displacements are then converted into ADPs. A series of such calculations were performed with different quantum chemical methods and basis sets on the three zwitterionic amino-acid structures of L-alanine, L-cysteine and L-threonine, where high-quality low-temperature X-ray data are available. To scale and compare calculated ADPs, X-ray ADPs from invariom refinement were used. The future use of calculated ADPs will include the investigation of systematic errors in experimental X-ray diffraction data. Completion of an isotropic structural model is already possible. Calculated ADPs might also make it possible to perform charge-density studies on data sets of limited resolution/coverage as obtained from weak scatterers, high-pressure measurements or to deconvolute electron density obtained from the maximum-entropy method.