Molecular Chiroptical Properties

One of the major goals of our research group is the development of highlevel ab initioquantum chemical models for prediction of molecular chiroptical properties such as specific rotation angles and CD spectra. Over the past several years, we have developed an efficient implementation of the coupledcluster singles and double (CCSD) linearresponse model that is applicable to mediumsized molecules such as [4]triangulane. These models are available as part of the PSI3 suite of quantum chemical programs.
Local Correlation and Molecular Response Properties
Local correlation, a concept pioneered by Pulay and Saebø, provides one possible route over the scaling wall through a judicious choice of molecular orbital basis. The "canonical" MO's, although convenient, are often delocalized over the entire molecular framework and often lead to overestimation of electronic interactions on spatially distant atoms. Pulay and Saebø demonstrated that if one abandons canonical orbitals and instead chooses a more localized form, vast numbers of electronic wavefunction parameters become negligible and may thus be ignored.

However, the application of the localization concept to molecular response properties introduces an additional complication: accurate representation of the derivative of the wave function with respect to an external perturbation, such as an electric or magnetic field, requires a more accurate representation of the unperturbed wave function than is necessary for computing the energy alone. Thus, the usual "orbital domain" structure that has performed so admirably for locally correlated groundstate energy calculations fails when applied to response properties. To compensate, we have devised a new domain construction approach based on analysis of the response of the individual molecular orbitals to the relevant external fields. This approach has proven successful for simple dipole polarizabilities, and work is underway to extend it to mixed electric/magnetic properties, such as optical rotation.