Vibrational circular dichroism from ab initio molecular dynamics and nuclear velocity perturbation theory in the liquid phase

2016 ◽  
Vol 145 (8) ◽  
pp. 084101 ◽  
Author(s):  
Arne Scherrer ◽  
Rodolphe Vuilleumier ◽  
Daniel Sebastiani
Keyword(s):  
Molecular Dynamics ◽  
Perturbation Theory ◽  
Circular Dichroism ◽  
Liquid Phase ◽  
Ab Initio ◽  
Vibrational Circular Dichroism ◽  
Ab Initio Molecular Dynamics ◽  
Velocity Perturbation ◽  
Circular Dichroïsm

The important role of non-covalent interactions for the vibrational circular dichroism of lactic acid in aqueous solution

2021 ◽  
Author(s):  
Sascha Jähnigen ◽  
Daniel Sebastiani ◽  
Rodolphe Vuilleumier
Keyword(s):  
Lactic Acid ◽  
Circular Dichroism ◽  
Computational Study ◽  
Bulk Water ◽  
Vibrational Circular Dichroism ◽  
Ab Initio Molecular Dynamics ◽  
Non Covalent Interactions ◽  
Circular Dichroïsm ◽  
Covalent Interactions

We present a computational study of vibrational circular dichroism (VCD) in solutions of (S)-lactic acid, relying on ab initio molecular dynamics (AIMD) and full solvation with bulk water. We discuss...

Electronic and Vibrational Circular Dichroism of Model β-Lactams: 3-Methyl- and 4-Methylazetidin-2-one

1996 ◽  
Vol 50 (5) ◽  
pp. 630-641 ◽  
Author(s):  
Jennifer McCann ◽  
Arvi Rauk ◽  
Gennadii V. Shustov ◽  
Hal Wieser ◽  
Danya Yang
Keyword(s):  
Circular Dichroism ◽  
Ab Initio ◽  
Electronic Transition ◽  
Vibrational Circular Dichroism ◽  
Protic Solvent ◽  
Free Energies ◽  
Chiroptical Properties ◽  
Circular Dichroïsm ◽  
Rotational Strengths ◽  
Simple Modeling

The chiroptical properties of the simplest chiral β-lactams, 3- and 4-methylazetidin-2-one, 1 and 2, respectively, were investigated. The experimental vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra were measured and compared with ab initio predictions. Both compounds were found to form dimers with calculated binding enthalpies and free energies of about −51 kJ/mol and −6 to −8 kJ/mol, respectively. The experimentally measured IR and VCD spectra were measured in concentrated nonpolar (CCl4) solution and are in agreement with the predicted IR and VCD spectra of the dimeric forms, 12 and 22, but not the monomers. The most intense dimer VCD bands originate from in-plane N-H wags, which perturb the H-bonded cyclic array. At the more dilute concentrations employed for the ECD spectra, the experimental ECD spectra in heptane were interpreted satisfactorily as arising from a mixture consisting predominantly of monomers. In protic solvent (H2O, MeOH), the ECD spectra are consistent with H-bonded monomers. Simple modeling suggests that the rotational strengths of the first electronic transition gain most of their intensity from the nonplanarity of the amide chromophore, the contributions of which follow a spiral rule previously enunciated.

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