  The polyalanine-based peptide series Ac-Ala_n-LysH+ (n=5-20) is a prime
example that a secondary structure motif which is well-known from the solution
phase (here: helices) can be formed in vacuo. We here revisit this conclusion
for n=5,10,15, using density-functional theory (van der Waals corrected
generalized gradient approximation), and gas-phase infrared vibrational
spectroscopy. For the longer molecules (n=10,15) \alpha-helical models provide
good qualitative agreement (theory vs. experiment) already in the harmonic
approximation. For n=5, the lowest energy conformer is not a simple helix, but
competes closely with \alpha-helical motifs at 300K. Close agreement between
infrared spectra from experiment and ab initio molecular dynamics (including
anharmonic effects) supports our findings.
