On the vibrational spectra of HSO and SOH

The harmonic and fundamental vibrational frequencies, rotational constants, vibration–rotation corrections and Zero point energies of HSO and SOH and their deuterated isomers (DSO and SOD) have been determined employing the CCSD(T) methodology in conjunction with the aug-cc-pV(X+d)Z and cc-pwCVQZ basis sets. The calculated fundamental frequencies of SOH are 830, 1150 and 3577 cm−1, for the υSO, υbend and υOH, respectively. In the case of HSO the computed fundamentals are 1002, 1077 and 2335 cm−1, for the υSO, υbend and υSH, respectively. The values are discussed in terms of the experimental determinations available. The rotational constants reported for HSO are in reasonable agreement with experiment; the computed values are 301,271, 20,557 and 19,192 MHz. In the case of SOH, for the first time, we report the rotational constants including vibration–rotation corrections, they are: 654,236, 16,621, 16,178 MHz. The force fields calculated allowed as to estimate accurate ZPEs, the suggested values are 6.48 and 8.19 kcal/mol for HSO and SOH, respectively. Finally, we recommend the following structural parameters for HSO rSO = 1.4924 Å, rSH = 1.3649 Å and ∠HSO = 104.76°; whereas for SOH we recommend rSO = 1.6302 Å, rOH = 0.9629 Å and ∠SOH = 107.97°.