Essential-State Model for Polymethine Dyes: Symmetry Breaking and Optical Spectra

Terenziani, Francesca; Przhonska, Olga V.; Webster, Scott; Padilha, Lázaro A.; Slominsky, Yuriy L.; Davydenko, Iryna; Gerasov, Andriy O.; Kovtun, Yuriy P.; Shandura, Mykola P.; Kachkovski, A.D.; Hagan, David J.; Stryland, Eric W. Van; Painelli, Anna

doi:10.1021/jz100430x

Cited by 95 publications

(174 citation statements)

References 19 publications

(58 reference statements)

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“…17,18 Alternatively, it has been noted that the inclusion of these states facilitates the quantitative parameterization of the dipole observables associated with the low-lying transitions. 23,24 In any case, the charge carrier on the bridge in the "intermediate" structures is frequently taken to have the character of a hole for cationic dyes such as in Scheme 1. 17,18,23 Diabatic states such as in Scheme 1 have more recently been invoked in theories of the nonlinear optical response of conjugated organic dyes.…”

Section: Introductionmentioning

confidence: 99%

“…23,24 In any case, the charge carrier on the bridge in the "intermediate" structures is frequently taken to have the character of a hole for cationic dyes such as in Scheme 1. 17,18,23 Diabatic states such as in Scheme 1 have more recently been invoked in theories of the nonlinear optical response of conjugated organic dyes. 25,26 Resonancetheoretic models of the electronic structure of dyes have very a) seth.olsen@uq.edu.au.…”

Section: Introductionmentioning

confidence: 99%

“…23,24,27,28 Resonance-theoretic models have been proven successful in the description of spectroscopic experiments. 19,20,[22][23][24][27][28][29] In order to learn the most from these successes, it would be useful to better understand the nature and justification of the approximate electronic structure implied by Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

“…The diabatic states can be identified with the bonding structures invoked in resonance-based theories of the optical response of organic dyes. 19,20,[22][23][24][27][28][29] We will use the analogies established between the electronic structures for the dyes in Scheme 1 to infer a parametric relationship between the diabatic Hamiltonians for the different dyes. The Hamiltonians extracted from the quantum chemical calculations can be approximately described by a one-parameter family.…”

Section: Introductionmentioning

confidence: 99%

“…This result qualitatively conflicts with some previous three-state models of the optoelectronic response of cyanine-like dyes. 23,24 The paper is organized as follows. Section II describes the computational protocol used to generate the quantum chemical data, and describes a general three-state framework that we will use for the analysis of this data.…”

Section: Introductionmentioning

confidence: 99%

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A three-state effective Hamiltonian for symmetric cationic diarylmethanes

Olsen

McKenzie

2012

The Journal of Chemical Physics

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Comparison of density functionals for energy and structural differences between the high-[ 5 T 2g :(t 2g ) 4 (e g ) 2 ] and low-[ 1 A 1g :(t 2g ) 6 (e g ) 0 ] spin states of iron (II) We analyze the low-energy electronic structure of a series of symmetric cationic diarylmethanes, which are bridge-substituted derivatives of Michler's Hydrol Blue. We use a four-electron, threeorbital complete active space self-consistent field and multi-state multi-reference perturbation theory model to calculate a three-state diabatic effective Hamiltonian for each dye in the series. We exploit an isolobal analogy between the active spaces of the self-consistent field solutions for each dye to represent the electronic structure in a set of analogous diabatic states. The diabatic states can be identified with the bonding structures in classical resonance-theoretic models of cyanine dyes. We identify diabatic states with opposing charge and bond-order localization, analogous to the classical resonance structures, and a third state with charge on the bridge. While the left-and right-charged structures are similar for all dyes, the structure of the bridge-charged diabatic state, and the Hamiltonian matrix elements connected to it, change significantly across the series. The change is correlated with an inversion of the sign of the charge carrier on the bridge, which changes from an electron pair to a hole as the series is traversed.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A three-state effective Hamiltonian for symmetric cationic diarylmethanes

Olsen

McKenzie

2012

The Journal of Chemical Physics

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25th Anniversary Article: Design of Polymethine Dyes for All‐Optical Switching Applications: Guidance from Theoretical and Computational Studies

et al. 2013

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All-optical switching--controlling light with light--has the potential to meet the ever-increasing demand for data transmission bandwidth. The development of organic π-conjugated molecular materials with the requisite properties for all-optical switching applications has long proven to be a significant challenge. However, recent advances demonstrate that polymethine dyes have the potential to meet the necessary requirements. In this review, we explore the theoretical underpinnings that guide the design of π-conjugated materials for all-optical switching applications. We underline, from a computational chemistry standpoint, the relationships among chemical structure, electronic structure, and optical properties that make polymethines such promising materials.

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Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

et al. 2016

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Symmetry-breaking charge transfer upon photoexcitation of al inear A-p-D-p-A molecule (D and Ab eing electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopyb ym onitoring the CN stretching modes on the Aunits.W hereas in apolar solvents,the S 1 state remains symmetric and quadrupolar,s ymmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands,instead of one in apolar solvents,w ith as plitting that increases with polarity.I np rotic solvents,s ymmetry breaking is significantly amplified by H-bonding interactions,which are the strongest at the CN group with the highest basicity.I ns trongly protic solvents,the two CN bands transform in about 20 ps into new bands with al arger splitting,a nd the lifetime of the S 1 state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.Scheme 1. Structure of ADA.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under http://dx.

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Essential-State Model for Polymethine Dyes: Symmetry Breaking and Optical Spectra

Cited by 95 publications

References 19 publications

A three-state effective Hamiltonian for symmetric cationic diarylmethanes

A three-state effective Hamiltonian for symmetric cationic diarylmethanes

25th Anniversary Article: Design of Polymethine Dyes for All‐Optical Switching Applications: Guidance from Theoretical and Computational Studies

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

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