X-ray circular dichroism signals: a unique probe of local molecular chirality

Zhang, Yu; Rouxel, Jérémy R.; Autschbach, Jochen; Govind, Niranjan; Mukamel, Shaul

doi:10.1039/c7sc01347g

Cited by 38 publications

(53 citation statements)

References 85 publications

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“…Originindependent optical rotation and rotatory strength tensors can also be calculated with the LR-TDDFT module within the gauge including atomic orbital (GIAO) basis formulation. 62,[102][103][104] Extensions to compute excited-state couplings are currently underway and will be available in a future release.…”

Section: Time-dependent Density Functional Theorymentioning

confidence: 99%

NWChem: Past, present, and future

Aprà

Bylaska

Jong

et al. 2020

The Journal of Chemical Physics

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Specialized computational chemistry packages have permanently reshaped the landscape of chemical and materials science by providing tools to support and guide experimental efforts and for the prediction of atomistic and electronic properties. In this regard, electronic structure packages have played a special role by using first-principle-driven methodologies to model complex chemical and materials processes. Over the past few decades, the rapid development of computing technologies and the tremendous increase in computational power have offered a unique chance to study complex transformations using sophisticated and predictive many-body techniques that describe correlated behavior of electrons in molecular and condensed phase systems at different levels of theory. In enabling these simulations, novel parallel algorithms have been able to take advantage of computational resources to address the polynomial scaling of electronic structure methods. In this paper, we briefly review the NWChem computational chemistry suite, including its history, design principles, parallel tools, current capabilities, outreach, and outlook.

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Section: Time-dependent Density Functional Theorymentioning

confidence: 99%

NWChem: Past, present, and future

Aprà

Bylaska

Jong

et al. 2020

The Journal of Chemical Physics

Self Cite

518

289

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“…Our next step is to identify the molecule-specific enantio-sensitive structure in Eqs. (7) and (8). That is, we will be looking for molecule-specific pseudoscalars; quantities that change sign upon parity inversion.…”

Section: A Photoelectron Circular Dichroismmentioning

confidence: 99%

“…Firstly, one can rely on using a strong laser field to enhance the magnetic-dipole transitions and interfere them against the electric-dipole ones, as done in chiral high harmonic generation [4][5][6][7]. Secondly, one can decrease the pitch of the light helix by using XUV/X-ray light [8,9]. Yet, in both cases the chiral signal would be equal to zero within the electric-dipole approximation.…”

Section: Introductionmentioning

confidence: 99%

Generalized perspective on chiral measurements without magnetic interactions

2018

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We present a unified description of several methods of chiral discrimination based exclusively on electric-dipole interactions. It includes photoelectron circular dichroism (PECD), enantio-sensitive microwave spectroscopy (EMWS), photoexcitation circular dichroism (PXCD) and photoelectron-photoexcitation circular dichroism (PXECD). We show that, in spite of the fact that the physics underlying the appearance of a chiral response is very different in all these methods, the enantio-sensitive and dichroic observable in all cases has a unique form. It is a polar vector given by the product of (i) a molecular pseudoscalar and (ii) a field pseudovector specified by the configuration of the electric fields interacting with the isotropic ensemble of chiral molecules. The molecular pseudoscalar is a rotationally invariant property, which is composed from different molecule-specific vectors and in the simplest case is a triple product of such vectors. The key property that enables the chiral response is the non-coplanarity of the vectors forming such triple product. The key property that enables chiral detection without relying on the chirality of the electromagnetic fields is the vectorial nature of the enantio-sensitive observable. Our compact and general expression for this observable shows what ultimately determines the efficiency of the chiral signal and if, or when, it can reach 100%. We also discuss the differences between the two phenomena, which rely on the bound states, PXCD and EMWS, and the two phenomena using the continuum states, PECD and PXECD. Finally, we extend these methods to arbitrary polarizations of the electric fields used to induce and probe the chiral response.

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“…chemical reactions, at their natural time scales. Other promising time-resolved chiroptical approaches developed in the last few years include vibrational circular dichroism spectroscopy [42], Coulomb explosion imaging [43,44], microwave detection [45], chiral-sensitive 2D spectroscopy [46], ultrafast resonant X-ray spectroscopy [47,48], time-resolved photoelectron circular dichroism [49] and photoexcitation circular dichroism [50].…”

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confidence: 99%

Strong-field control and enhancement of chiral response in bi-elliptical high-order harmonic generation: an analytical model

Ayuso

Decleva

Patchkovskii

et al. 2018

J. Phys. B: At. Mol. Opt. Phys.

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The generation of high-order harmonics in a medium of chiral molecules driven by intense bielliptical laser fields can lead to strong chiroptical response in a broad range of harmonic numbers and ellipticities [D. Ayuso et al, J. Phys. B 51, 06LT01 (2018)]. Here we present a comprehensive analytical model that can describe the most relevant features arising in the high-order harmonic spectra of chiral molecules driven by strong bi-elliptical fields. Our model recovers the physical picture underlying chiral high-order harmonic generation based on ultrafast chiral hole motion and identifies the rotationally invariant molecular pseudoscalars responsible for chiral dynamics. Using the chiral molecule propylene oxide as an example, we show that one can control and enhance the chiral response in bi-elliptical high-order harmonic generation by tailoring the driving field, in particular by tuning its frequency, intensity and ellipticity, exploiting a suppression mechanism of achiral background based on the linear Stark effect. arXiv:1803.04952v2 [physics.optics]

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X-ray circular dichroism signals: a unique probe of local molecular chirality

Abstract: X-ray circular dichroism (XCD) spectroscopy provides a powerful tool to detect subtle electronic structures of chiral molecules.

Cited by 38 publications

References 85 publications

NWChem: Past, present, and future

NWChem: Past, present, and future

Generalized perspective on chiral measurements without magnetic interactions

Strong-field control and enhancement of chiral response in bi-elliptical high-order harmonic generation: an analytical model

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