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Ab initio calculations of vibronic activity in phosphorescence microwave double resonance spectra of para-dichlorobenzene
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.
KTH, School of Biotechnology (BIO), Theoretical Chemistry.ORCID iD: 0000-0002-1763-9383
2005 (English)In: Theoretical Chemistry accounts, ISSN 1432-881X, E-ISSN 1432-2234, Vol. 113, no 1, 15-27 p.Article in journal (Refereed) Published
Abstract [en]

The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet-triplet (B-3(1u)->(1)A(g)) transition through a number of vibronic subbands. The second order spin-orbit coupling (SOC) contribution to the spin splitting of the B-3(1u) ((3)pi pi*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin-spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.

Place, publisher, year, edition, pages
2005. Vol. 113, no 1, 15-27 p.
Keyword [en]
phosphorescence microwave double resonance spectra; vibronic activity; p-dichlorobenzene; quadratic response methodology; zero-field splitting parameters
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-5084DOI: 10.1007/s00214-004-0596-xISI: 000227633400002Scopus ID: 2-s2.0-14644440780OAI: oai:DiVA.org:kth-5084DiVA: diva2:7839
Note
QC 20100825Available from: 2005-04-28 Created: 2005-04-28 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Charge-transfer excitations and phtophysical properties of molecular building blocks
Open this publication in new window or tab >>Charge-transfer excitations and phtophysical properties of molecular building blocks
2005 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis reports a state-of-the-art theoretical study of photophysical properties of organic charge-transfer aromatic molecules. These molecules are building blocks of molecular functional materials used in modern photonics technology and play essential roles in chemistry and biology in general. A good understanding of these systems is thus important.

The theoretical results for permanent dipole moments of some substituted benzenes have been obtained using the coupled cluster singles and doubles (CCSD) method. The performance of density functional theory (DFT) for the geometry and electronic properties has been compared with that of traditional ab initio methods, such as Hartree-Fock, second-order Möller Plesset perturbation theory (MP2), CCSD and CCSD(T). Limitations of the DFT methods for charge transfer molecules have been demonstrated. The multi-configuration self-consistent field (MCSCF) method has been applied to understand properties of the triplet states of benzene derivatives by studying their phosphorescence with the inclusion of contributions from vibronic coupling. It has also been employed to calculate the photophysics of the thioxanthone molecule containing three benzene rings in combination with the CASPT2 method, resolving a long-standing problem concerning the possible stable conformations of the molecule.

With knowledge of the building blocks a series of porphyrin derivatives with exceptionally large two-photon absorption cross sections were designed, and proposed for use in bioimaging applications. The static and dynamic properties of a few zinc and platinum organometallic compounds, being possible candidates for optical limiting devices, have also investigated.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. 43 p.
Series
Theses in philosophy from the Royal Institute of Technology, ISSN 1654-627X
Keyword
Theoretical chemistry, Photophysical porperties, CCSD, CASSCF, Teoretisk kemi
National Category
Theoretical Chemistry
Identifiers
urn:nbn:se:kth:diva-184 (URN)91-7178-020-3 (ISBN)
Public defence
2005-05-12, FA32, Albanova centrum, 10:00
Opponent
Supervisors
Note
QC 20101011Available from: 2005-04-28 Created: 2005-04-28 Last updated: 2011-11-23Bibliographically approved

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