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Two-photon absorption of hydrogen-bonded octupolar molecule clusters
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
Department of Physics, Linyi Normal University.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0001-8198-9284
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-1763-9383
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2008 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 112, no 14, 4387-4392 p.Article in journal (Refereed) Published
Abstract [en]

Charge-transfer octupolar molecules can form clusters in solution through intermolecular hydrogen bonds. In the present work we explore the role of such clustering on two-photon absorption (TPA) spectra assuming 1,3,5-triamino-2,4,6- trinitrobenzene (TATB) as a model system. Using density functional quadratic response theory we examine different cluster structures of TATB dimers, trimers, and tetramers taken from snapshots of molecular dynamics simulations. In comparison with the TPA spectrum of a monomer, significant red shifts of charge-transfer states are predicted for all chosen clusters, which mainly is the result of the distortion of the structures induced by the aggregation. The TPA spectra for dimers and trimers show strong conformation dependence, whereas they turn out to be more stable for tetramers. Enhancements of TPA absorption have also been found for clusters containing less distorted molecules connected by hydrogen bonds.

Place, publisher, year, edition, pages
2008. Vol. 112, no 14, 4387-4392 p.
Keyword [en]
Absorption; Astrophysics; Binding sites; Density functional theory; Dimers; Dynamics; Hydrogen; Light absorption; Luminescence of organic solids; Molecular dynamics; Molecules; Monomers; Multiphoton processes; Oligomers; Optical materials; Photons; Quantum chemistry; American Chemical Society (ACS); Charge transfer state (CTS); charge transfers; cluster structures; Density-functional (DF); Distorted molecules; Distortion (deformation); form clusters; Intermolecular hydrogen bonds; model systems; Molecular dynamics simulations (MDS); molecule clusters; octupolar molecules; Quadratic response (QR); red shifting; Tetramers; TPA spectra; Trinitrobenzene; Two-photon absorption (TPA) spectra; Two-photon-absorption (TPA)
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-7957DOI: 10.1021/jp712118wISI: 000254659900033Scopus ID: 2-s2.0-46449138465OAI: oai:DiVA.org:kth-7957DiVA: diva2:13146
Note
QC 20100823. Uppdaterad från accepted till published (20100823). Tidigare titel: Two-photon absorption of hydrogen bonded octupolar molecular clustersAvailable from: 2008-02-05 Created: 2008-02-05 Last updated: 2010-08-23Bibliographically approved
In thesis
1. Theoretical Characterization of Optical Processes in Modecular Complexes
Open this publication in new window or tab >>Theoretical Characterization of Optical Processes in Modecular Complexes
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The main theme of this thesis is to study effects of different environments on geometric and electronic structures, as well as optical responses, of molecules using time-(in)dependent density functional theory. Theoretical calculations have been carried out for properties that can be measured by conventional and advanced experimental techniques, including one-photon absorption (OPA), two-photon absorption (TPA), surface-enhanced Raman scattering (SERS) and second order nonlinear optical (NLO) response. The obtained good agreement between the theory and the experiment allows to further extract useful information about inter- and intra-molecular interactions that are not accessible experimentally.

By comparing calculated one-photon absorption spectra of aluminum phthalocyanine chloride (AlPcCl) and AlPcCl -water complexes with the corresponding experiments, detailed information about the interaction between water molecules and AlPcCl, and geometric changes of AlPcCl molecule has been obtained. Effects of aggregation on two-photon absorption spectra of octupolar molecules have been examined. It is shown that the formation of clusters through inter-molecular hydrogen bonding can drastically change profiles of TPA spectra. It has also demonstrated that a well designed molecular aggregate/cluster, dendrimer, can enhance the second order nonlinear optical response of the molecules. In collaboration with experimentalists, a series of end-capped triply branched dendritic chromophores have been characterized, which can lead to large enhancement of the second order NLO property when the dipoles of the three branches in the dendrimers are highly parallelized.

Surface-enhanced Raman scattering has made the detection of single molecules on metal surface become possible. Chemically bonded molecule-metal systems have been extensively studied. We have shown in a joint experimental and theoretical work that stable Raman spectra of a non-bonding molecule, perylene, physically adsorbed on Ag nano-particles can also be observed at low temperature. It is found that the local enhanced field has a tendency to drive molecule toward a gap of two closely lying nano-particles. The trapped molecule can thus provide a stable Raman spectrum with high resolution when its thermal motion is reduced at low temperature.

For the ever growing size of molecular complexes, there is always the need to develop new computational methods. A conceptually simple but computationally efficient method, named as central insertion scheme (CIS), is proposed that allows to calculate electronic structure of quasi-periodic system containing more than 100,000 electrons at density functional theory levels. It enables to monitor the evolution of electronic structure with respect to the size of the system.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. 60 p.
Keyword
one-photon absorption, two-photon absorption, surface-enhanced Raman scattering
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-4629 (URN)978-91-7178-857-3 (ISBN)
Public defence
2008-02-25, FA32, Roslagstullsbacken 21, AlbaNova University Center, Stockholm, 14:00
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Note
QC 20100823Available from: 2008-02-05 Created: 2008-02-05 Last updated: 2010-08-23Bibliographically approved

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