Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

摘要

The rotational spectrum of phosphaethene (CH2PH) was reinvestigated. One hundred and nineteen new lines were measured in the submillimeter range from 500 to 650 GHz. The determination of the centrifugal distortion constants is significantly improved. As the molecule is close to symmetric prolate top, both reduction A and S were compared. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-zeta quality and a core correlation correction. The structure of CHZPH was compared to that of CH2NH which was also determined for this goal. It is found that the semi-experimental structure of CH2NH is less accurate than the ab initio structure. It is also found that the methylene group is much more asymmetric in CH2NH than in CH2PH. 2006 Elsevier Inc. All rights reserved.