Chirality-Induced Spin Selectivity in a Coarse-Grained Tight-Binding Model for Helicene

Matthias Geyer, Rafael Gutierrez, Vladimiro Mujica, Gianaurelio Cuniberti

Research output: Contribution to journalArticle

Abstract

Spin-dependent effects in helical molecular systems, leading to the so-called chirality-induced spin selectivity (CISS) effect, have strongly attracted the attention of the chemical and physical community over the past few years. A large amount of experimental material has been collected so far, and different theoretical approaches have been presented to rationalize the CISS effect. The problem is, however, still a subject of debate. We present a semianalytical coarse-grained atomistic description of the electronic structure of a simple helical molecule, including spin-orbit interactions. For reference, we consider helicene, which is a pure carbon-based helical system with no chiral centers, and which has been previously shown experimentally to display a CISS effect. Our model exploits perturbation theory and a Löwdin-like partitioning to obtain an effective Ï-πHamiltonian, where all coupling coefficients depend on the helical geometry and predefined Slater-Koster parameters. As a result, they can be explicitly computed, thus providing physically meaningful orders of magnitude. We further discuss the conditions under which a nonvanishing spin polarization can be obtained in the model. We expect that our approach will serve to bridge the gap between purely phenomenological model Hamiltonians and more advanced first-principles methodologies.

Original languageEnglish (US)
Pages (from-to)27230-27241
Number of pages12
JournalJournal of Physical Chemistry C
Volume123
Issue number44
DOIs
StatePublished - Nov 7 2019

Fingerprint

Chirality
chirality
Hamiltonians
selectivity
Spin polarization
Electronic structure
Orbits
Carbon
coupling coefficients
Molecules
spin-orbit interactions
Geometry
perturbation theory
methodology
electronic structure
carbon
polarization
geometry
molecules

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Chirality-Induced Spin Selectivity in a Coarse-Grained Tight-Binding Model for Helicene. / Geyer, Matthias; Gutierrez, Rafael; Mujica, Vladimiro; Cuniberti, Gianaurelio.

In: Journal of Physical Chemistry C, Vol. 123, No. 44, 07.11.2019, p. 27230-27241.

Research output: Contribution to journalArticle

Geyer, Matthias ; Gutierrez, Rafael ; Mujica, Vladimiro ; Cuniberti, Gianaurelio. / Chirality-Induced Spin Selectivity in a Coarse-Grained Tight-Binding Model for Helicene. In: Journal of Physical Chemistry C. 2019 ; Vol. 123, No. 44. pp. 27230-27241.
@article{f25de935804e4ccab1796fed0536bf65,
title = "Chirality-Induced Spin Selectivity in a Coarse-Grained Tight-Binding Model for Helicene",
abstract = "Spin-dependent effects in helical molecular systems, leading to the so-called chirality-induced spin selectivity (CISS) effect, have strongly attracted the attention of the chemical and physical community over the past few years. A large amount of experimental material has been collected so far, and different theoretical approaches have been presented to rationalize the CISS effect. The problem is, however, still a subject of debate. We present a semianalytical coarse-grained atomistic description of the electronic structure of a simple helical molecule, including spin-orbit interactions. For reference, we consider helicene, which is a pure carbon-based helical system with no chiral centers, and which has been previously shown experimentally to display a CISS effect. Our model exploits perturbation theory and a L{\"o}wdin-like partitioning to obtain an effective {\"I}-πHamiltonian, where all coupling coefficients depend on the helical geometry and predefined Slater-Koster parameters. As a result, they can be explicitly computed, thus providing physically meaningful orders of magnitude. We further discuss the conditions under which a nonvanishing spin polarization can be obtained in the model. We expect that our approach will serve to bridge the gap between purely phenomenological model Hamiltonians and more advanced first-principles methodologies.",
author = "Matthias Geyer and Rafael Gutierrez and Vladimiro Mujica and Gianaurelio Cuniberti",
year = "2019",
month = "11",
day = "7",
doi = "10.1021/acs.jpcc.9b07764",
language = "English (US)",
volume = "123",
pages = "27230--27241",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "44",

}

TY - JOUR

T1 - Chirality-Induced Spin Selectivity in a Coarse-Grained Tight-Binding Model for Helicene

AU - Geyer, Matthias

AU - Gutierrez, Rafael

AU - Mujica, Vladimiro

AU - Cuniberti, Gianaurelio

PY - 2019/11/7

Y1 - 2019/11/7

N2 - Spin-dependent effects in helical molecular systems, leading to the so-called chirality-induced spin selectivity (CISS) effect, have strongly attracted the attention of the chemical and physical community over the past few years. A large amount of experimental material has been collected so far, and different theoretical approaches have been presented to rationalize the CISS effect. The problem is, however, still a subject of debate. We present a semianalytical coarse-grained atomistic description of the electronic structure of a simple helical molecule, including spin-orbit interactions. For reference, we consider helicene, which is a pure carbon-based helical system with no chiral centers, and which has been previously shown experimentally to display a CISS effect. Our model exploits perturbation theory and a Löwdin-like partitioning to obtain an effective Ï-πHamiltonian, where all coupling coefficients depend on the helical geometry and predefined Slater-Koster parameters. As a result, they can be explicitly computed, thus providing physically meaningful orders of magnitude. We further discuss the conditions under which a nonvanishing spin polarization can be obtained in the model. We expect that our approach will serve to bridge the gap between purely phenomenological model Hamiltonians and more advanced first-principles methodologies.

AB - Spin-dependent effects in helical molecular systems, leading to the so-called chirality-induced spin selectivity (CISS) effect, have strongly attracted the attention of the chemical and physical community over the past few years. A large amount of experimental material has been collected so far, and different theoretical approaches have been presented to rationalize the CISS effect. The problem is, however, still a subject of debate. We present a semianalytical coarse-grained atomistic description of the electronic structure of a simple helical molecule, including spin-orbit interactions. For reference, we consider helicene, which is a pure carbon-based helical system with no chiral centers, and which has been previously shown experimentally to display a CISS effect. Our model exploits perturbation theory and a Löwdin-like partitioning to obtain an effective Ï-πHamiltonian, where all coupling coefficients depend on the helical geometry and predefined Slater-Koster parameters. As a result, they can be explicitly computed, thus providing physically meaningful orders of magnitude. We further discuss the conditions under which a nonvanishing spin polarization can be obtained in the model. We expect that our approach will serve to bridge the gap between purely phenomenological model Hamiltonians and more advanced first-principles methodologies.

UR - http://www.scopus.com/inward/record.url?scp=85074425094&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85074425094&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b07764

DO - 10.1021/acs.jpcc.9b07764

M3 - Article

AN - SCOPUS:85074425094

VL - 123

SP - 27230

EP - 27241

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 44

ER -