Velocity-dependent property surfaces and the theory of vibrational circular dichroism

Buckingham, A. D.; Fowler, Patrick W.; Galwas, P.A.

doi:10.1016/0301-0104(87)85017-6

Cited by 178 publications

(66 citation statements)

References 34 publications

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“…From the theoretical point of view [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21], the BornOppenheimer (BO) [22], or adiabatic, treatment of the coupled motion of electrons and nuclei in molecular systems is inadequate for predicting VCD. Since the intensity of the VCD signal is proportional to the rotational strength for a transition between two vibrational states, the calculation of the electric current and of the magnetic dipole moment (and of their scalar product) is required.…”

Section: Introductionmentioning

confidence: 99%

Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Scherrer

Agostini

Sebastiani

et al. 2015

The Journal of Chemical Physics

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The nuclear velocity perturbation theory (NVPT) for vibrational circular dichroism (VCD) is derived from the exact factorization of the electron-nuclear wave function. This new formalism offers an exact starting point to include correction terms to the Born-Oppenheimer (BO) form of the molecular wave function, similarly to the complete-adiabatic approximation. The corrections depend on a small parameter that, in a classical treatment of the nuclei, is identified as the nuclear velocity. Apart from proposing a rigorous basis for the NVPT, we show that the rotational strengths, related to the intensity of the VCD signal, contain a new contribution beyond-BO that can be evaluated with the NVPT and that only arises when the exact factorization approach is employed. Numerical results are presented for chiral and non-chiral systems to test the validity of the approach.

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Section: Introductionmentioning

confidence: 99%

Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Scherrer

Agostini

Sebastiani

et al. 2015

The Journal of Chemical Physics

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“…(13), µ G is the dipole moment of the ground state. For neutral systems and exact wave functions these tensors obey the following sum rules [13]:…”

Section: Theorymentioning

confidence: 99%

A vibrational circular dichroism implementation within a Slater-type-orbital based density functional framework and its application to hexa- and hepta-helicenes

et al. 2007

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We describe the implementation of the rotational strengths for vibrational circular dichroism (VCD) in the Slater-type orbital based Amsterdam Density Functional (ADF) package. We show that our implementation, which makes use of analytical derivative techniques and London atomic orbitals, yields origin independent rotational strengths. The basis set dependence in the particular case of Slater-type basis functions is also discussed. It turns out that the triple zeta STO basis sets with one set of polarization functions (TZP) are adequate for VCD calculations. The origindependence of the atomic axial tensors is checked by a distributed origin gauge implementation. The distributed and common origin gauge implementations yield virtually identical atomic axial tensors with the Slatertype basis sets employed here, proving that our implementation yields origin independent rotational strengths. We verify the implementation for a set of benchmark molecules, for which the dependence of the VCD spectra on the particular choice of the exchangecorrelation functional is studied. The pure functionals BP86 and OLYP show a particularly good performance. Then, we apply this approach to study the VCD spectra of hexa-and hepta-helicenes. In particular we focus on relationships between the sign of the rotational strengths of the two helicenes.

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“…Electric dipole strengths derived from eq. [3] are formally equivalent to the Atomic Polar Tensor (APT) theory. Stephens circumvents the summation over excited states in eq.…”

Section: N= I Experimental Detailsmentioning

confidence: 99%

“…The coincident introduction of chiroptical techniques in the form of vibrational circular dichroism (VCD) spectroscopy and the Raman equivalent (ROA) has promised further insights. Extraction of the inherent information from the latter techniques (and to some extent the former) has been hampered by theoretical difficulties which have largely been overcome with the introduction of practical nonempirical formalisms by Nafie and Freedman (I), Stephens (2), and Buckingham, Fowler, and Galwas (3) and their computer implementations by Stephens and coworkers (4), Morokuma and Sugeta ( 3 ,and Dutler (6), Yang (7,8), and Rauk (6)(7)(8). An ab initio approximate model, LMO-VCD (9), implemented by Polavarapu (10) has also proved to be effective.…”

Section: Introductionmentioning

confidence: 99%

The vibrational circular dichroism spectra of 2-methylaziridine: dominance of the asymmetric centre at nitrogen

Rauk¹,

Eggimann²,

Wieser³

et al. 1994

Can. J. Chem.

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The experimental VCD spectrum of (2R)-2-methylaziridine has been measured in the region 800–1500 cm−1. The ab initio implementation of the Vibronic Coupling Theory (VCT) of Nafie and Freedman, using the 6-31G*(0.3) basis set, in the common origin and distributed origin gauges and with uniformly and optimally scaled quantum mechanical force fields, is used to investigate the chiroptical properties. VCD spectra are computed for both cis and trans invertomers. The predicted VCD spectrum of 2-methylaziridine (the equilibrium mixture) is dominated by that of the trans diastereomer, not simply because of its greater abundance but because the rotatory strengths of many absorptions in the mid-IR are oppositely signed and of similar magnitude in the two invertomers which differ in absolute configuration at nitrogen. The VCD spectrum of 2-methylaziridine is compared in detail to that of 2-methyloxirane. In the region of the methyl group deformations and CH2 scissor, the theoretical (R)-2-methyloxirane VCD spectrum displays a much closer similarity to the cis-(2R)-2-methylaziridine than to the trans diastereomer.

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Velocity-dependent property surfaces and the theory of vibrational circular dichroism

Cited by 178 publications

References 34 publications

Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

Nuclear velocity perturbation theory for vibrational circular dichroism: An approach based on the exact factorization of the electron-nuclear wave function

A vibrational circular dichroism implementation within a Slater-type-orbital based density functional framework and its application to hexa- and hepta-helicenes

The vibrational circular dichroism spectra of 2-methylaziridine: dominance of the asymmetric centre at nitrogen

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