An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2
Abstract
We present the results of ab initio calculations for the lower electronic states of the Group 15 (pnictogen) dihydrides, SbH2 and BiH2. For each of these molecules the two lowest electronic states become degenerate at linearity and are therefore subject to the Renner effect. Spin-orbit coupling is also strong in these two heavy-element containing molecules. For the lowest two electronic states of SbH2, we construct the three dimensional potential energy surfaces and corresponding dipole moment and transition moment surfaces by multi-reference configuration interaction techniques. Including both the Renner effect and spin-orbit coupling, we calculate term values and simulate the rovibrational and rovibronic spectra of SbH2. Excellent agreement is obtained with the results of matrix isolation infrared spectroscopic studies and with gas phase electronic spectroscopic studies in absorption. For the heavier dihydride BiH2 we calculate bending potential curves and the spin-orbit coupling con...stant for comparison. For SbH2 we further study the local mode vibrational behavior and the formation of rovibronic energy level clusters in high angular momentum states.
Keywords:
SbH2 / BiH2 / Ab initio 3D potential energy surfaces / Renner effect / Spin-orbit coupling / Rovibrational spectra / Local mode vibrations / Rovibronic energy level clusteringSource:
Journal of Molecular Spectroscopy, 2016, 330, 130-141Publisher:
- Academic Press Inc Elsevier Science, San Diego
Funding / projects:
- The study of physicochemical and biochemical processes in living environment that have impacts on pollution and the investigation of possibilities for minimizing the consequences (RS-172001)
- Deutsche Forschungsgemeinschaft
- Fonds der Chemischen Industrie
Note:
- The peer-reviewed version: https://cer.ihtm.bg.ac.rs/handle/123456789/4311
Related info:
DOI: 10.1016/j.jms.2016.03.004
ISSN: 0022-2852
WoS: 000390634600017
Scopus: 2-s2.0-85003516089
Collections
Institution/Community
IHTMTY - JOUR AU - Ostojić, Bojana AU - Schwerdtfeger, Peter AU - Bunker, P. R. AU - Jensen, Per PY - 2016 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1904 AB - We present the results of ab initio calculations for the lower electronic states of the Group 15 (pnictogen) dihydrides, SbH2 and BiH2. For each of these molecules the two lowest electronic states become degenerate at linearity and are therefore subject to the Renner effect. Spin-orbit coupling is also strong in these two heavy-element containing molecules. For the lowest two electronic states of SbH2, we construct the three dimensional potential energy surfaces and corresponding dipole moment and transition moment surfaces by multi-reference configuration interaction techniques. Including both the Renner effect and spin-orbit coupling, we calculate term values and simulate the rovibrational and rovibronic spectra of SbH2. Excellent agreement is obtained with the results of matrix isolation infrared spectroscopic studies and with gas phase electronic spectroscopic studies in absorption. For the heavier dihydride BiH2 we calculate bending potential curves and the spin-orbit coupling constant for comparison. For SbH2 we further study the local mode vibrational behavior and the formation of rovibronic energy level clusters in high angular momentum states. PB - Academic Press Inc Elsevier Science, San Diego T2 - Journal of Molecular Spectroscopy T1 - An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2 VL - 330 SP - 130 EP - 141 DO - 10.1016/j.jms.2016.03.004 ER -
@article{ author = "Ostojić, Bojana and Schwerdtfeger, Peter and Bunker, P. R. and Jensen, Per", year = "2016", abstract = "We present the results of ab initio calculations for the lower electronic states of the Group 15 (pnictogen) dihydrides, SbH2 and BiH2. For each of these molecules the two lowest electronic states become degenerate at linearity and are therefore subject to the Renner effect. Spin-orbit coupling is also strong in these two heavy-element containing molecules. For the lowest two electronic states of SbH2, we construct the three dimensional potential energy surfaces and corresponding dipole moment and transition moment surfaces by multi-reference configuration interaction techniques. Including both the Renner effect and spin-orbit coupling, we calculate term values and simulate the rovibrational and rovibronic spectra of SbH2. Excellent agreement is obtained with the results of matrix isolation infrared spectroscopic studies and with gas phase electronic spectroscopic studies in absorption. For the heavier dihydride BiH2 we calculate bending potential curves and the spin-orbit coupling constant for comparison. For SbH2 we further study the local mode vibrational behavior and the formation of rovibronic energy level clusters in high angular momentum states.", publisher = "Academic Press Inc Elsevier Science, San Diego", journal = "Journal of Molecular Spectroscopy", title = "An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2", volume = "330", pages = "130-141", doi = "10.1016/j.jms.2016.03.004" }
Ostojić, B., Schwerdtfeger, P., Bunker, P. R.,& Jensen, P.. (2016). An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2. in Journal of Molecular Spectroscopy Academic Press Inc Elsevier Science, San Diego., 330, 130-141. https://doi.org/10.1016/j.jms.2016.03.004
Ostojić B, Schwerdtfeger P, Bunker PR, Jensen P. An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2. in Journal of Molecular Spectroscopy. 2016;330:130-141. doi:10.1016/j.jms.2016.03.004 .
Ostojić, Bojana, Schwerdtfeger, Peter, Bunker, P. R., Jensen, Per, "An ab initio study of SbH2 and BiH2: The Renner effect, spin-orbit coupling, local mode vibrations and rovibronic energy level clustering in SbH2" in Journal of Molecular Spectroscopy, 330 (2016):130-141, https://doi.org/10.1016/j.jms.2016.03.004 . .