Jump to main content
Jump to site search


Effect of puckering motion and hydrogen bond formation on the vibrational circular dichroism spectrum of a flexible molecule: the case of (S)-1-indanol

Author affiliations

Abstract

The influence of flexibility and hydrogen bond formation on the IR absorption and vibrational circular dichroism (VCD) spectrum of a floppy protic molecule, namely, (S)-1-indanol, is studied in both non-polar CCl4 and polar DMSO solvents. The experimental IR absorption and VCD spectra obtained by Fourier transform spectroscopy are interpreted using both static density functional theory (DFT) calculations and first principles molecular dynamics (FPMD) within DFT, using the nuclear velocity perturbation theory (NVPT). Simulation of the spectra based on static optimised geometries is not sufficient in CCl4 and going beyond static calculations is mandatory for satisfactorily reproducing the VCD spectra. The FPMD results obtained in DMSO indicate that (S)-1-indanol is hydrogen-bonded to one DMSO molecule. As a result, static “cluster-in-the-bulk” DFT calculations in which the solute–solvent interaction is modeled as the most stable (S)-1-indanol:DMSO complexes in a DMSO continuum yield satisfactory agreement with the experiment. Correspondence between experimental and simulated spectra is slightly improved when the VCD spectrum is calculated as the summed contributions of snapshots extracted from FPMD trajectories, due to better sampling of the potential-energy surface. Finally, NVPT calculations further improve the description of experimental spectra by taking into account higher-energy structures, which are not necessary local minima.

Graphical abstract: Effect of puckering motion and hydrogen bond formation on the vibrational circular dichroism spectrum of a flexible molecule: the case of (S)-1-indanol

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Mar 2018, accepted on 08 May 2018 and first published on 09 May 2018


Article type: Paper
DOI: 10.1039/C8CP01695J
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
  •   Request permissions

    Effect of puckering motion and hydrogen bond formation on the vibrational circular dichroism spectrum of a flexible molecule: the case of (S)-1-indanol

    K. Le Barbu-Debus, A. Scherrer, A. Bouchet, D. Sebastiani, R. Vuilleumier and A. Zehnacker, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP01695J

Search articles by author

Spotlight

Advertisements