Abstract
A method for population and bonding analyses in the calculations with extended basis sets is proposed. The definition and evaluation method of the atomic orbitals in molecular environments (AOIMs) are described. It is shown that the AOIMs can be divided into two subsets, the strongly occupied minimal compact subset {AOIM}B and the very weakly occupied “Rydberg” subset {AOIM}R, according to the orbital population obtained from Mulliken analysis with AOIMs as basis sets. The viewpoint of “molecular orbitals consisting of minimal atomic orbital sets” can be optimally realized in terms of {AOIM}B. The Mulliken population based on AOIMs is reasonable and fairly stable to changes of basis sets. The Mayer bond orders calculated based on {AOIM}B are quite stable to the changes of basis sets; therefore they can be used to measure objectively the contribution of individual atomic orbitals to bonding.
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
