Gauge-origin independent multiconfigurational self-consistent-field theory for vibrational circular dichroism

Bak, Keld L.; Jo, Poul; rgensen,; Helgaker, Trygve; Ruud, Kenneth; Jo, Hans; Jensen, rgen Aa.

doi:10.1063/1.464445

Cited by 188 publications

(83 citation statements)

References 32 publications

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“…38 Also, like infrared absorption (IR) spectra, VCD spectra of molecules in a particular conformational state can be modeled theoretically using quantum chemical methods. [47][48][49][50][51] VCD spectral characteristics of -turns in linear [52][53][54] and disulfide-cyclized 53 tetrapeptides and longer natural [55][56][57] and model 54,58 sequences have been studied. The VCD spectrum of a disulfide-cyclized type II -turn has been proposed previously by Wyssbrod and Diem.…”

Section: -28mentioning

confidence: 99%

Optical spectroscopic elucidation of β‐turns in disulfide bridged cyclic tetrapeptides

2006

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Vibrational circular dichroism (VCD) spectroscopic features of type II β‐turns were characterized previously, but, criteria for differentiation between β‐turn types had not been established yet. Model tetrapeptides, cyclized through a disulfide bridge, were designed on the basis of previous experimental results and the observed incidence of amino acid residues in the i + 1 and i + 2 positions in β‐turns, to determine the features of VCD spectra of type I and II β‐turns. The results were correlated with electronic circular dichroism (ECD) spectra and VCD spectra calculated from conformational data obtained by molecular dynamics (MD) simulations. All cyclic tetrapeptides yielded VCD signals with a higher frequency negative and a lower frequency positive couplet with negative lobes overlapping. MD simulations confirmed the conformational homogeneity of these peptides in solution. Comparison with ECD spectroscopy, MD, and quantum chemical calculation results suggested that the low frequency component of VCD spectra originating from the tertiary amide vibrations could be used to distinguish between types of β‐turn structures. On the basis of this observation, VCD spectroscopic features of type II and VIII β‐turns and ECD spectroscopic properties of a type VIII β‐turn were suggested. The need for independent experimental as well as theoretical investigations to obtain decisive conformational information was recognized. © 2006 Wiley Periodicals, Inc. Biopolymers 85: 1–11, 2007.This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com

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Section: -28mentioning

confidence: 99%

Optical spectroscopic elucidation of β‐turns in disulfide bridged cyclic tetrapeptides

2006

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“…(25) the calculation of the electronic contribution of the AATs requires knowledge of the unitary matrices U (1),R λα and U (1),H β , including their occupied-occupied (occ-occ) blocks and the unperturbed eigenvectors, C. The integrals χ (1),R λα a | χ (1),H β b , χ (1),R λα a |χ b , and χ a |χ (1),H β b are calculated numerically using London atomic orbitals (LAOs) as basis functions. An LAO is obtained from a field independent basis function by adding a phase factor that depends on the magnetic field [17][18][19][20]:…”

Section: The Atomic Axial Tensormentioning

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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“…London orbitals depend explicitly on the magnetic field induction, and are correct to first order in the external field induction for one-electron atomic systems. 29 In addition to ensuring originindependent results for finite basis sets for variational methods, the use of London orbitals also often leads to faster basis set convergence. 30 An alternative is to express the electric dipole operator in the velocity gauge.…”

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.

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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.

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Gauge-origin independent multiconfigurational self-consistent-field theory for vibrational circular dichroism

Cited by 188 publications

References 32 publications

Optical spectroscopic elucidation of β‐turns in disulfide bridged cyclic tetrapeptides

Optical spectroscopic elucidation of β‐turns in disulfide bridged cyclic tetrapeptides

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

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

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