A charge–charge flux–dipole flux decomposition of the dipole moment derivatives and infrared intensities of the AB3 (A = N,P; B = H,F) molecules |
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| Institution: | 1. Instituto de Química, Universidade Estadual de Campinas, CP 6154, 13083-970 Campinas-SP, Brazil;2. Instituto de Química de São Carlos, Universidade de São Paulo, CP 780, 13560-970, São Carlos-SP, Brazil;1. Department of Physics, Faculty of Arts and Sciences, Ondokuz May?s University, TR-55139 Kurupelit-Samsun, Turkey;2. Department of Chemistry, Faculty of Arts and Science, Sinop University, TR-57000 Sinop, Turkey;1. Institute of Chemistry, Department of Analytical Chemistry, University of Campinas, P.O. Box 6154, 13083-970 Campinas, SP, Brazil;2. School of Civil Engineering, Architecture and Urban Design, University of Campinas, P.O. Box 6143, 13083-889 Campinas, SP, Brazil;1. Department of Chemical & Environmental Engineering, University of Arizona, 1133 E. James E. Rogers Way, Harshbarger 108, Tucson, AZ 85721, United States;2. Agilent Technologies Inc., 2850 Centerville Rd., Wilmington, DE 19808, United States;3. Metrohm USA Inc, Houston, TX 77034, United States;1. Department of Clinical Laboratory, Jinhua Central Hospital, Jinhua, Zhejiang 321000, China;2. Department of Clinical Laboratory, Beijing Northern Hospital of Weaponry Industry, Beijing 100089, China;3. Centre of Laboratory Medicine, Zhejiang Provincial People’s Hospital, People’s Hospital of Hangzhou Medical College, 158 Shangtang Road, Hangzhou, Zhejiang 310014, China;1. Institute of Microbiology and Epizootics, Centre for Infection Medicine, Department of Veterinary Medicine, Freie Universität Berlin, Berlin, Germany;2. Advanced Light and Electron Microscopy (ZBS-4), Robert Koch Institute, Berlin, Germany;3. National Institute for Public Health and the Environment (RIVM), Centre for Infectious Disease Control (CIb), Bilthoven, the Netherlands;4. Institute of Medical Microbiology, University Hospital Münster, Münster, Germany;5. Institute of Hygiene, DRK Kliniken Berlin, Berlin, Germany;1. Department of Infectious Diseases, Sir Run Run Shaw Hospital, College of Medicine, Zhejiang University, Hangzhou, Zhejiang 310016, China;2. Department of Clinical Laboratory, Jinhu Central Hospital, Jinhua, Zhejiang 321000, China;3. Blood Center of Zhejiang Province, 789 Jianye Road, Hangzhou, Zhejiang 310052, China;4. Centre of Laboratory Medicine, Zhejiang Provincial People''s Hospital, People''s Hospital of Hangzhou Medical College, 158 Shangtang Road, Hangzhou, Zhejiang 310014, China |
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| Abstract: | The quantum theory of atoms in molecules (AIM) has been used to decompose dipole moment derivatives and fundamental infrared intensities of the AB3 (A = N,P; B = H,F) molecules into charge–charge flux–dipole flux (CCFDF) contributions. Calculations were carried out at the MP2(FC)/6-311++G(3d,3p) level. Infrared intensities calculated from the AIM atomic charges and atomic dipoles are within 13.8 km mol?1 of the experimental values not considering the NH3 and PH3 stretching vibrations for which the experimental bands are severely overlapped. Group V atomic dipoles are very important in determining the molecular dipole moments of NF3, PH3 and PF3 although the atomic charges account for almost all of the NH3 molecular moment. Dipole fluxes on the Group V atom are important in determining the stretching band intensities of all molecules whereas they make small contributions to the bending mode intensities. Consideration of dipole flux contributions from the terminal atoms must also be made for accurately describing the intensities of all these molecules. As expected from a simple bond moment model, charge contributions dominate for most of the NH3, NF3, and PF3 dipole moment derivatives and intensities. Charge flux and dipole flux contributions are very substantial for all the PH3 vibrations, cancelling each other for the stretching modes and reinforcing one another for the bending modes. |
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