Stretching vibrational band intensities of XH3 （X=N, Sb） molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model. The dipole moment surfaces of NH...Stretching vibrational band intensities of XH3 （X=N, Sb） molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model. The dipole moment surfaces of NH3 and SbH3 are calculated with the density functional theory and at the correlated MP2 level, respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides （NH3, PH3, AsH3 and SbH3） are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.展开更多
基金jointly supported by the National Natural Science Foundation of China(No.22273093,No.41905018,No.21903080)the Ministry of Science and Technology of China(No.2022YFF0606500)。
基金supported by the National Natural Science Foundation of China(No.22125302,No.22173099,No.22288201,No.21873089,and No.21973037)the Guangdong Science and Technology Program(No.2019ZT08L455 and No.2019JC01X091)the Shenzhen Science and Technology Program(No.ZDSYS20200421111001787).
基金This work was supported by the National Basic Research Program of China （No.2013BAK12B00 and No.2013CB834602） and the National Natural Science Foundation of China （No.21225314 and No.21427804）.
基金ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation （No.21225314 and No.20903085）, the National Basic Research Program of China （No.2013CB834602） and the Fundamental Research Funds for the Central Universities.
基金This work was supported by the National Key Basic Research Program of China （2013CB834602 and 2013BAK12B02）, and the National Natural Science Foundation of China （No.21473172, No.21411130183, No.21303176）.
基金This work is supported by the National Natural Science Foundation of China （No.20903085）, the NKBRSF 2010CB9230, and RFBR-Russia （No.06-05- 39016）. The support of the Groupement de Recherche International SAMIA （Spectroscopie d＇Absorption des Mol@cules d＇Interet Atmospherique） between CNRS （France）, RFBR （Russia） and CAS （China） is also acknowledged.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 20103007 and 20473079）.
文摘Stretching vibrational band intensities of XH3 （X=N, Sb） molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model. The dipole moment surfaces of NH3 and SbH3 are calculated with the density functional theory and at the correlated MP2 level, respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides （NH3, PH3, AsH3 and SbH3） are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.
基金supported by the National Natural Science Foundation of China (No.21688102, No.91436209, and No.21427804)the Chinese Academy of Science (No.XDB21020100)
