Natural Chiroptical Spectroscopy: Theory and Computations

Hansen, Aage E.; Bouman, Thomas D.

doi:10.1002/9780470142639.ch5

Cited by 157 publications

(59 citation statements)

References 314 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[11] for the (2S) enantiomer converts to b = À0.0281 au at a wavelength of 589.3 nm (w = 0.07732 au). Calculated OR tensors for this molecule are provided in Table 1 for the standard orientation (SO) center of nuclear charge (CNC) geometry and for nuclear coordinates displaced by a vector (5,4,5) . The calculated isotropic GIAO OR parameter of b = À0.0257 agrees quite well with the b derived from experiment.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Autschbach

2011

ChemPhysChem

124

View full text Add to dashboard Cite

An approach to calculate origin-independent electronic chiroptical property tensors using time-dependent density functional theory (TDDFT) and gauge-including atomic orbital (GIAO) basis sets is evaluated. Computations of origin-dependent optical rotation tensors and of rotatory strengths needed to simulate circular dichroism spectra are presented. The optical rotation tensor computations employ solutions of coupled perturbed Kohn-Sham equations for a dynamic electric field and a static magnetic field. Because the magnetic field is time independent, the GIAO treatment is somewhat simplified compared to a previously reported method, at some added computational cost if hybrid functionals are employed. GIAO rotatory strengths are also calculated, using transition density matrices from a standard TDDFT excitation energy module. A new implementation in the NWChem quantum chemistry package is employed for representative computations of origin-invariant chiroptical response tensors for methyloxirane, norbornenone, and the ketosteroid androstadienone. For the steroid molecule the vibrational structure of the CD spectrum is modeled explicitly by using calculated Franck-Condon factors. The agreement with experiment is favorable.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Density functional theory (DFT) and time-dependent DFT (TDDFT) belong to this class of methods. Another approach that has found applications in chiroptical response computations is to adopt the velocity gauge for the electric moments; [5][6][7] see ref. [8] for further details.…”

Section: Introductionmentioning

confidence: 99%

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Autschbach

2011

ChemPhysChem

124

View full text Add to dashboard Cite

show abstract

“…2, 4, 6, 8, and 10). [52][53][54][55][56][57][58][59][60][61][62][63][64][65] Exploratory calculations on eremophilane and related lactones indicated that the overall appearance of the simulated CD spectra was dominated by the configuration at C 8 . 66 Inverting the configuration at C 2 , the overall shape and the positions of the maximum and minimum on the wavelength scale of the simulated CD spectrum of compound 8 remained almost unchanged apart from slight differences concerning the amplitude (Fig.…”

Section: Calculated Structural Properties Electronic Excitation Enermentioning

confidence: 99%

Absolute configuration of eremophilane sesquiterpenes from Petasites hybridus: Comparison of experimental and calculated circular dichroism spectra

Bodensieck¹,

Fabian²,

Kunert³

et al. 2009

Chirality

View full text Add to dashboard Cite

In-depth conformational analyses of 10 known eremophilane (= (1S,4aR,7R,8aR)-decahydro-1,8a-dimethyl-7-(1-methylethyl)napththalene) sesquiterpenes, 1-10, from Petasites hybridus were performed with molecular mechanics as well as density functional theory methods. Electronic transition energies and rotational strengths of these eight eremophilane lactones and two petasins were calculated by time-dependent density functional theory (B3PW91/TZVP). The absolute configurations of the constituents could be assigned by comparison of their simulated and experimental circular dichroism (CD) spectra in methanol as (4S,5R,8S,10R) (1, 2), (2R,4S,5R,8S,10R) (3, 4, 5), (2R,4S,5R,8R,9R,10R) (6), (2R,4S,5R,8R,10R) (7, 8), and (3R,4R,5R) (9, 10). Single-crystal X-ray diffraction data of 8beta-hydroxyeremophilanolide ((8S)-8-hydroxyeremophil-7(11)-en-12,8-olide) (1) served as starting point for the theoretical conformational calculations of the 8beta-epimers of the eremophilane lactones. Experimental CD spectra as well as (1)H NMR spectra of compound 1 in methanol were considerably dependent on sample concentration.

show abstract

“…30 An alternative is to express the electric dipole operator in the velocity gauge. 23,31,32 This approach gives gauge origin-independent results for non-variational methods, but often at the cost of slower basis set convergence.…”

Section: -6mentioning

confidence: 99%

Open-Ended Recursive Calculation of Single Residues of Response Functions for Perturbation-Dependent Basis Sets

Friese

Ringholm

Gao

et al. 2015

J. Chem. Theory Comput.

View full text Add to dashboard Cite

We present theory, implementation and applications of a recursive scheme for the calculation of single residues of response functions which can treat perturbations that affect the basis set. This scheme enables the calculation of non-linear light absorption properties to arbitrary order for other perturbations than the electric field. We apply this scheme for the first treatment of two-photon circular dichroism (TPCD) using London orbitals at the Hartree-Fock level of theory. In general TPCD calculations suffer from the problem of origin dependence which has so far been solved by using the velocity gauge for the electric dipole operator. This work now enables comparison of results from London orbital and velocity gauge based TPCD calculations. We find that the results from the two approaches both exhibit strong basis set dependence but that they are very similar with respect to their basis set convergence.

show abstract

Natural Chiroptical Spectroscopy: Theory and Computations

Cited by 157 publications

References 314 publications

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Absolute configuration of eremophilane sesquiterpenes from Petasites hybridus: Comparison of experimental and calculated circular dichroism spectra

Open-Ended Recursive Calculation of Single Residues of Response Functions for Perturbation-Dependent Basis Sets

Contact Info

Product

Resources

About