Towards a scalable and accurate quantum approach for describing vibrations of molecule–metal interfaces

• David M. Benoit,
• Bruno Madebene,
• Inga Ulusoy,
• Luis Mancera,
• Yohann Scribano and
• Sergey Chulkov

Beilstein J. Nanotechnol. 2011, 2, 427–447, doi:10.3762/bjnano.2.48

• ; vibrational theory; Introduction The study of molecular vibrations has been a topic of continued interest in chemistry for over a century, starting with the work of William Coblenz in 1905. The main driving force behind these studies has been the correlation that exists between molecular structure and

• Hamiltonians, as vibrational spectra probe bond strengths directly. Unfortunately, standard vibrational theory is often powerless to explain the subtle changes observed in the vibrational spectrum when a molecule undergoes a conformational change or is adsorbed on a surface. Indeed, the harmonic approximation

• the VSCF/VCI level of vibrational theory and using the STA approach we obtain 3477 cm−1 which corresponds to a shift of −135 cm−1 from the gas-phase molecule stretch frequency, ν(HF) = 3612 cm−1 from the 1-D vibrational solutions. To the best of our knowledge the HF-stretch frequency of hydrogen