Vibrational circular dichroism calculations

Bak KL, Jtirgensen P, Helgaker T, Ruud K (1994) Basis set convergence and correlation effects in vibrational circular dichroism calculations using London atomic orbitals. Faraday Discuss 99 121-129... 

Danya Yang and Arvi Rauk, The A Priori Calculation of Vibrational Circular Dichroism Intensities. 

Stephens PJ, Pan JJ, Krohn K. Determination of the Absolute Configurations of Pharmacological Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism The New Cytotoxic Iridoid Piismatomerin. Journal of Organic Chemistry 2007 72(20) 7641-7649. 

Computational efforts to describe the conformational preferences of (R,R)-tartaric acid and its derivatives - mainly for isolated molecules - were made recently [18-25]. The conformations of these molecules also attracted attention from experimental chemists [22-40]. (/ ,/ [-tartaric acid and its dimethyl diester were observed in crystals, in conformations with extended carbon chain and planar a-hydroxy-carboxylic moieties (T.v.v and Tas for the acid and the ester, respectively) [25-28] (see Figure 2). The predominance ofthe T-structure was also shown by studies of optical rotation [31], vibrational circular dichroism (VCD) [23], Raman optical activity [32, 35], and nuclear magnetic resonance (NMR) [22, 33, 34]. The results of ab-initio and semiempirical calculations indicated that for the isolated molecules the Tsv and T as conformers were those of lowest energy [22, 21, 23, 25]. It should be noted, however, that early interpretations of NMR and VCD studies indicated that for the dimethyl diester of (/ ,/ [-tartaric acid the G+ conformation is favored [36-38]. 

R. Dutler and A. Rauk,/. Am. Chem. Soc., Ill, 6957 (1989). Calculated Infrared Absorption and Vibrational Circular Dichroism Intensities of Oxirane and its Deuterated Analogs. 

Finally, we remark that the problem of the calculation of molecular quantities directly comparable with the outcome of experiments in the liquid phase is not limited to the realm of the NLO processes. All experiments involving the interaction of light with molecules in condensed matter are plagued by this problem. The methodology reviewed here has been applied (with appropriate modifications) to various spectroscopies, IR [23], Raman [24], Surface Enhanced Raman Scattering (SERS) [25], vibrational circular dichroism (VCD) [26] and linear dichroism [27] with equal reliability, and other extensions will come. 

Dutler R, Rauk A (1989) Calculated infrared-absorption and vibrational circular-dichroism intensities of oxirane and its deuterated analogs. J Am Chem Soc 111 6957-6966... 

Freedman TB, Cao XL, Young DA et al (2002) Density functional theory calculations of vibrational circular dichroism in transition metal complexes Identification of solution conformations and mode of chloride ion association for (+)-tris(ethylenediaminato)cobalt (III). J Phys Chem A 106 3560-3565... 

Dobler, J. Peters, N. Larsson, C. Bergman, A Geidel, E. Hiihnerfuss, H., The absolute structures of separated PCB-methylsulfone enantiomers determined by vibrational circular dichroism and quantum mechanical calculations J. Molec. Struct. (Theochem) 2002, 586, 159-166. 

Stephens, P. J. Pan, J. J. Krohn, K. Determination of the absolute configurations of pharmacological natural products via density functional theory calculations of vibrational circular dichroism the bew cytotoxic iridoidprismatomerin, / Org. Chem. 2007, 72, 7641-7649. 

We have developed a simple physical model suggesting that for most, if not all, chiral macromolecules, their terahertz absorption will be accompanied by terahertz circular dichroism. Ab initio methods have been used to successfully calculate the vibrational circular dichroism spectra of small molecules, however, these models have largely focused on spectra in the near-infrared, spectra dominated by bond stretching and bending, and the wagging of small... 

Recenfly fhe ah initio calculation mefhod of vibrational circular dichroism (VCD), optical rotatory dispersion (ORD), and electronic circular dichroism (ECD) has been developed as fhe third nonempirical method [3, 4]. The method is applicable to compounds having no chromophore, and so should be widely used in future. 

Stephens PJ, Devlin FJ, Chabalowski CF, Frisch MJ. Ab initio calculation of vibrational circular dichroism spectra using density functional force fields. J Phys Chem 1994 ... 

Bak KL, Bludsky O, Jorgensen P. Ab initio calculations of anharmonic vibrational circular dichroism intensities of /ran.v-2,3-didcutcrio-oxiranc. J Chem Phys 1995 103 10548-10555. 

PJ Stephens, FJ Devlin, CS Ashvar, CF Chabalowski, MJ Frisch. Theoretical Calculation of Vibrational Circular Dichroism Spectra. Faraday Discuss 99 103-119, 1994. 

Abstract The Vibrational Circular Dichroism (VCD) spectroscopy has been developing rapidly in both experimental and theoretical aspects. Currently, the VCD has become one of the most effective and reliable spectroscopic technique to determine the absolute configuration of chiral molecules. Its success is related to the availability of instrumentation and software for quantum-chemical calculation of the spectra. Nowadays, large parts of the VCD spectra can be trustfully predicted by theory and critically verified by confiding experiment, and vice versa. In the last decade, several theoretical and experimental VCD studies reported on VCD chirality transfer phenomenon occurring when an achiral molecule becomes VCD active as a result of intermolecular interactions with a chiral one. There are still some theoretical and experimental uncertainties about the VCD chirality transfer, however, benefits from an comprehensive use of the phenomenon can push our ability to diversify the intermolecular complexes and deepen our understanding of intermolecular interactions. This chapter is a review of the computational studies on VCD chirality transfer phenomenon supported by the experimental references, and ended by perspectives. 

Nicu VP (2009) Implementation, calculation and interpretation of vibrational circular dichroism spectra. PhD Dissertation, Viije Universiteit... 

Devlin FJ, Stephens PJ (1994) Ab initio calculation of vibrational circular dichroism spectra of chiral natural products using MP2 force fields camphor. J Am Chem Soc 116 5003—5(X)4... 

---