Ab initio molecular geometry and anharmonic vibrational spectra of thiourea and thiourea‐d 4

• Published in: Journal of computational chemistry Vol. 32; no. 4; pp. 718 - 729
• Main Author: Kowal, Andrzej T.
• Format: Journal Article
• Language: English
• Published: 01.03.2011
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.21665

Abstract Potential energy surface (PES) of thiourea, SC(NH 2 ) 2, has been searched for stable conformers under C 1 , C s , C 2 , and C 2v symmetry constraints by post‐Hartree–Fock ab initio methods with electron correlation level varying from second‐order Moeller–Plesset perturbation theory (MP2) to quadratic configuration interaction with single and double excitations (QCISD) and basis sets of double‐ and triple‐zeta quality within 6‐31+G(d,p) to aug‐cc‐pVTZ range. Thiourea conformers of C 2 and C s symmetry have been found as stationary points on the PES with no imaginary frequencies at MP2/6‐31+G(d,p) level, whereas only the C 2 conformer seems as true minimum when basis sets containing more polarization and/or diffuse functions were used. At QCISD/cc‐pVTZ level, only the C 2 thiourea conformer has been found as true minimum on the PES. Anharmonic vibrational spectra of C 2 conformers of thiourea and thiourea‐d 4 have been computed by vibrational self‐consistent field (VSCF) and correlation‐corrected VSCF methods using quartic force field approximation at MP2/TZV+(2d,2p), and MP2/6‐311+G(3df,2p) level and direct approach at MP2/6‐31+G(2d,p) level. Both quartic force field and direct VSCF methods used PES expansion in curvilinear (internal) coordinates. Wavenumbers of fundamental, first overtone, and combination transitions of C 2 symmetry conformer have been calculated for natural abundance thiourea and thiourea‐d 4 isotopomer. Anharmonic corrections originating from mean field and mode coupling effects vary from 5 to 60 cm −1 , whereas mode–mode correlation contribution seems significant in the case of ν(N‐H) stretching and δ(NH 2 ) deformation modes (15–5 cm −1 ). Application of internal coordinates in the VSCF calculation results in slight underestimation of δ(NH 2 ) deformation mode fundamentals and correct description of out‐of‐plane large‐amplitude τ(SCNH) modes. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011