Stretching vibrational overtone spectrum of arsine and stibine

A theoretical-spectroscopy, ab initio-based study of the electronic ground state of 121SbH3

“…[35] and with other theoretical values [35,44]. For all transitions with available, experimentally derived intensity values (Table 6), the present work has improved the agreement with experiment significantly relative to the previous calculations [35,44].…”

“…It is also generally accepted that for molecules with localmode character, the local-mode quantum numbers represent a more adequate labeling scheme for Tables 1 and 5 unless otherwise indicated. b Observed relative intensities [35]. c Calculated relative intensities [35].…”

“…In the infrared region, spectra of different vibrational bands for 121 SbH 3 and 123 SbH 3 were subsequently measured and analysed [34,35,36,37,38,39,40]; these works produced experimental values for vibrational term values up to 12000 cm −1 above the vibrational ground state with the largest number of vibrational states being investigated for 121 SbH 3 . Halonen et al [35] reported relative band intensities for stretching vibrational bands with up to four stretching quanta excited. Recently, the high-resolution infrared spectrum of 121 SbD 3 was recorded and various fundamental levels were characterized by Canè et al [27].…”

“…On the theoretical side, Halonen et al [34,35,37] complemented their experimental studies of stibine by computing vibrational energies by means of local-mode models. Another local mode analysis of the vibrational energies of stibine was carried out by means of the creation and annihilation operators technique [41,42].…”

“…This situation is usually resolved by adjusting the PES empirically in fits to experimental data. A number of 'spectroscopic' PESs of stibine [35,37,41,43] have been obtained by least-squares fitting to the available experimental band centers.…”