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WIREs Comput Mol Sci
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Vibrational circular dichroism

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This review focuses on the theoretical background of vibrational circular dichroism (VCD) spectroscopy. Besides discussing the first‐principle approaches of the theoretical evaluation of VCD spectra, practical computational considerations, such as the available electronic structure computational levels and program packages, are summarized. Illustrative examples are shown for the absolute configuration and conformation determination of mid‐sized molecules based on the comparison of calculated end experimental VCD spectra, including the comparison of the performance of different computational levels. The conformational analysis of larger biomolecules, such as carbohydrates, nucleotides, and peptides by VCD spectroscopy, and the theoretical simulation of solvent effects are also discussed. The review is concluded by a short summary of the present stage of the computation of VCD spectra and the expected future direction of theoretical developments. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 1 403–425 DOI: 10.1002/wcms.39

This article is categorized under:

  • Electronic Structure Theory > Ab Initio Electronic Structure Methods
Figure 1.

VCD spectrum of 3R‐(+)‐methylazetidin‐2‐one 1 measured in CCl4 solution (a) in comparison with the calculated spectrum of its H‐bonded cyclic dimer 12 (b) and the calculated spectra of the monomer (c–e) obtained at different levels of theory. The calculated frequencies are scaled by 0.9 (HF) or 0.95 (MP2, B3LYP) and are simulated with a Lorentzian band shape of 10 cm−1 full width at half‐height. (Reprinted with permission from Ref 41. Copyright 1996 Society for Applied Spectroscopy.)

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Figure 2.

Mid‐IR VCD spectrum of R‐(+)‐methyloxirane recorded in CCl4 solution in comparison with calculated spectra using the B3LYP functional with a range of basis sets (a) and the cc‐pVTZ basis set with a range of functionals (b). Band shapes are Lorentzian with 4 cm−1 full width at half‐height. Fundamentals are numbered. (Reprinted with permission from Ref 46. Copyright 2002 American Chemical Society.)

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Figure 3.

Structure of S‐(+)‐D3‐anti‐trans‐anti‐trans‐anti‐trans‐ perhydrophenylene 4.

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Figure 4.

Comparison of the B3LYP/TZ2P, B3PW91/TZ2P and experimental VCD spectra of 4. The bandshapes of the calculated spectra are Lorentzian with 4 cm−1 full width at half‐height. The numbers define the fundamental modes of 4 contributing to the spectral bands. (Reprinted with permission from Ref 50. Copyright 2007 Springer.)

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Figure 5.

Structure of S‐(+)‐tricarbonyl‐η6‐N‐pivaloyl‐ tetrahydroquinoline‐chromium(0) 5.

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Figure 6.

Comparison of the B3PW91/6–311++G(2d,2p) and B3LYP/6–311++G(2d,2p) VCD spectra of the lowest‐energy conformer of S5 to the experimental VCD spectrum of (+)‐5. Band shapes are Lorentzian with 4 cm−1 full width at half‐height. The numbers are those of the fundamentals. (Reprinted with permission from Ref 51. Copyright 2008 Elsevier.)

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Figure 7.

Structure of Δ and Λ enantiomers of metal complexes [M(III)(acac)3] (acac = acetylacetonato; M = Cr, Co, Ru, Rh, Ir, and Al) 6 and [M(III)(acac)2(dbm)] (dbm = dibenzoylmethanato; M = Cr, Co, and Ru) 7.

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Figure 8.

Experimental and calculated VCD spectra of a) 2‐deoxy‐α‐d‐xylopyranoside (CDCl3, 0.10 M, 100 μm CaF2 cell) and b) 2‐deoxy‐β‐d‐xylopyranoside (CDCl3, 0.10 M, 100 μm CaF2 cell). The theoretical spectra were obtained from the computed spectra of the individual conformers at the B3LYP/6–31G** level of theory by weighted averaging using the Boltzmann populations shown in parentheses. The glycoside band is shaded in the Figure. Conclusions on the VCD sign of the glycoside band are shown on panel c). (Reprinted with permission from Ref 54. Copyright 2007 Wiley‐VCH.)

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Figure 9.

VCD spectra of the d(CGCGCGCG) octanucleotide simulated for the MD (a) and regular X‐ray geometry with (b) and without (c) the solvent, as compared to the experimental spectrum (d). The base (left) and sugar‐phosphate (right) vibration regions are expanded separately. (Reprinted with permission from Ref 55. Copyright 2005 American Chemical Society.)

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Figure 10.

Simulated IR (left) and VCD (right) spectra of model dodecapeptides with (a) 310‐helical or (b) α‐helical structure. (Reprinted with permission from Ref 68. Copyright 2002 American Chemical Society.)

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Figure 11.

The effect of solvent model on the simulated amide I‐II VCD (b) and IR (c) absorption bands of model peptide Ac‐Aib‐Gly‐NHMe forming a type I′ β‐turn, computed at the BPW91/6–31G** level. The spectra were simulated for the optimized minimal hydration structure shown in (a) with seven explicit water molecules (solid line), for the COSMO solvent model (dotted) and for vacuum (dashed). (Reprinted with permission from Ref 75. Copyright 2008 Springer.)

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