The A1A –X1A electronic spectra of jet-cooled HPS and DPS have been observed for the first time, using a pulsed discharge jet source. Laser induced fluorescence spectra were obtained in the 850–650 nm region. Although the 000 band was not observed, strong 3n0 and 210 3n0 progressions and 31 hot bands could be assigned in the HPS LIF spectrum. Single vibronic level emission spectra were also recorded, resulting in the determination of all three HPS ground state vibrational frequencies. High level ab initio calculations were used to help confirm the vibronic assignments by calculation of transition energies, anharmonic vibrational frequencies, and anharmonic Franck-Condon factors. Ab initio potential energy surfaces gave an equilibrium structure for the X1A state of rPH = 1.4334 Å, rPS = 1.9373 Å, θ= 101.77◦ and for the A1A state of rPH = 1.4290 Å, rPS= 2.0635 Å, and θ = 91.74. The rotational contours observed are consistent with these structures, confirming that the bond angle of HPS decreases on electronic excitation. Although the bond angles of HNO and HNS open in the excited state, in accord with the Walsh predictions for 12 valence electron HAB molecules, HPO, HAsO and now HPS all show the opposite behavior.

An experimental and theoretical study of the electronic spectrum of HPS, a second row HNO analog

TARRONI, RICCARDO;
2013

Abstract

The A1A –X1A electronic spectra of jet-cooled HPS and DPS have been observed for the first time, using a pulsed discharge jet source. Laser induced fluorescence spectra were obtained in the 850–650 nm region. Although the 000 band was not observed, strong 3n0 and 210 3n0 progressions and 31 hot bands could be assigned in the HPS LIF spectrum. Single vibronic level emission spectra were also recorded, resulting in the determination of all three HPS ground state vibrational frequencies. High level ab initio calculations were used to help confirm the vibronic assignments by calculation of transition energies, anharmonic vibrational frequencies, and anharmonic Franck-Condon factors. Ab initio potential energy surfaces gave an equilibrium structure for the X1A state of rPH = 1.4334 Å, rPS = 1.9373 Å, θ= 101.77◦ and for the A1A state of rPH = 1.4290 Å, rPS= 2.0635 Å, and θ = 91.74. The rotational contours observed are consistent with these structures, confirming that the bond angle of HPS decreases on electronic excitation. Although the bond angles of HNO and HNS open in the excited state, in accord with the Walsh predictions for 12 valence electron HAB molecules, HPO, HAsO and now HPS all show the opposite behavior.
2013
Robert Grimminger; Dennis J. Clouthier; Riccardo Tarroni; Zhong Wang; Trevor J. Sears
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/202951
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