Ab initio molecular orbital calculations of the optical rotatory response of a single oriented water molecule are described. The unique tensor element gxy was computed to be -0.047 bohr3 with CCSD/6-311+G(d,p). A value of -0.033 was obtained with the minimal valence basis that was better suited to parsing the rotatory response among a limited number of excited states. Transition moments were calculated ab initio and qualitatively derived from the wave functions. Rotations were reckoned from the relative dispositions of the transition moments with respect to the wavevectors. In this way, it was possible to intuitively reckon the form of the optical rotation tensor consistent with that from higher levels of theory and to establish which excitations make the most significant contributions.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry