DOI: 10.1063/1.472719. Optical activity of electronically delocalized molecular aggregates: Nonlocal response formulation

Optical activity of electronically delocalized molecular aggregates: Nonlocal response formulation

10.1063/1.472719

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A unified description of circular dichroism and optical rotation in small optically active molecules, larger conjugated molecules, and molecular aggregates is developed using spatially nonlocal electric and magnetic optical response tensors χ(r,r′,ω). Making use of the time dependent Hartree Fock equations, we express these tensors in terms of delocalized electronic oscillators. We avoid the commonly-used long wavelength (dipole) approximation k⋅r≪1 and include the full multipolar form of the molecule–field interaction. The response of molecular aggregates is expressed in terms of monomer response functions. Intermolecular Coulomb interactions are rigorously taken into account thus eliminating the necessity to resort to the local field approximation or to a perturbative calculation of the aggregate wave functions. Applications to naphthalene dimers and trimers show significant corrections to the standard interacting point dipoles treatment.

Bibliography

Wagersreiter, T., & Mukamel, S. (1996). Optical activity of electronically delocalized molecular aggregates: Nonlocal response formulation. The Journal of Chemical Physics, 105(18), 7995â8010.

Authors 2

Thomas Wagersreiter (first)
Shaul Mukamel (additional)

References 50 Referenced 17

10.1080/10587259408039274 / Mol. Cryst. Liquid Cryst. (1994)
10.1002/adma.19950070408 / Adv. Mater. (1995)
10.1002/bip.1969.360070509 / Biopolymers (1969)
10.1002/bip.1976.360150110 / Biopolymers (1976)
10.1063/1.1840658 / J. Chem. Phys. (1967)
{'key': '2024021101074586700_r5', 'first-page': '3703', 'volume': '52', 'year': '1969', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1969)
10.1063/1.1671881 / J. Chem. Phys. (1969)
10.1107/S0108767386098732 / Acta Crystallogr. A (1986)
10.1107/S0021889886089823 / J. Appl. Cryst. (1986)
10.1021/bi00603a033 / Biochem. (1978)
10.1111/j.1751-1097.1985.tb01629.x / Photochem. Photobiol. (1985)
{'key': '2024021101074586700_r9b'}
{'key': '2024021101074586700_r10'}
10.1111/j.1751-1097.1985.tb01629.x / Photochem. Photobiol. (1985)
10.1021/bi00760a024 / Biochem. (1972)
{'key': '2024021101074586700_r13', 'first-page': '251', 'volume': '16', 'year': '1915', 'journal-title': 'Phys. Z.'} / Phys. Z. (1915)
{'key': '2024021101074586700_r13a'}
{'key': '2024021101074586700_r14', 'first-page': '1', 'volume': '48', 'year': '1915', 'journal-title': 'Ann. Phys.'} / Ann. Phys. (1915)
{'key': '2024021101074586700_r15', 'first-page': '161', 'volume': '52', 'year': '1928', 'journal-title': 'Z. Phys.'} / Z. Phys. (1928)
10.1017/S0305004100033211 / Proc. Cambridge. Philos. Soc. (1958)
10.1103/PhysRev.7.472 / Phys. Rev. (1916)
{'key': '2024021101074586700_r18', 'first-page': '453', 'volume': '38', 'year': '1927', 'journal-title': 'Rev. Gen. Sci. Pure Appliq.'} / Rev. Gen. Sci. Pure Appliq. (1927)
10.1098/rspa.1934.0075 / Proc. R. Soc. London, Ser. A (1934)
10.1063/1.1750060 / J. Chem. Phys. (1937)
10.1063/1.1730025 / J. Chem. Phys. (1959)
{'key': '2024021101074586700_r22', 'first-page': '2952', 'volume': '94', 'year': '1971', 'journal-title': 'J. Am. Chem. Soc.'} / J. Am. Chem. Soc. (1971)
10.1063/1.1678981 / J. Chem. Phys. (1973)
10.1063/1.437616 / J. Chem. Phys. (1979)
10.1063/1.1725879 / J. Chem. Phys. (1964)
10.1063/1.1697294 / J. Chem. Phys. (1965)
10.1103/RevModPhys.9.432 / Rev. Mod. Phys. (1937)
10.1021/cr60295a004 / Chem. Rev. (1975)
{'key': '2024021101074586700_r29'}
{'key': '2024021101074586700_r30'}
{'key': '2024021101074586700_r31'}
{'key': '2024021101074586700_r32'}
10.1063/1.464748 / J. Chem. Phys. (1993)
{'key': '2024021101074586700_r34', 'first-page': '9719', 'volume': '101', 'year': '1993', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1993)
10.1063/1.471427 / J. Chem. Phys. (1996)
{'key': '2024021101074586700_r36'}
{'key': '2024021101074586700_r37'}
{'key': '2024021101074586700_r38'}
10.1080/00268976800100051 / Mol. Phys. (1968)
{'key': '2024021101074586700_r40', 'volume': '1971', 'year': '1988.', 'journal-title': 'J. Chem. Soc. A'} / J. Chem. Soc. A (1988.)
10.1002/9780470143506.ch3 / Adv. Chem. Phys. (1962)
10.1063/1.467250 / J. Chem. Phys. (1994)
10.1103/PhysRevB.52.2528 / Phys. Rev. B. (1995)
10.1016/0009-2614(95)00542-C / Chem. Phys. Lett. (1995)
10.1063/1.1673504 / J. Chem. Phys. (1970)
10.1021/j100365a042 / J. Phys. Chem. (1990)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:15 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 8:08 p.m.)
Indexed	1 month, 2 weeks ago (July 12, 2025, 6:55 p.m.)
Issued	28 years, 9 months ago (Nov. 8, 1996)
Published	28 years, 9 months ago (Nov. 8, 1996)
Published Print	28 years, 9 months ago (Nov. 8, 1996)

Funders 0

None

BibTeX

@article{Wagersreiter_1996, title={Optical activity of electronically delocalized molecular aggregates: Nonlocal response formulation}, volume={105}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.472719}, DOI={10.1063/1.472719}, number={18}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Wagersreiter, Thomas and Mukamel, Shaul}, year={1996}, month=nov, pages={7995–8010} }

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