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@PHDTHESIS{Fatima:475303,
author = {Fatima, Mariyam},
othercontributors = {Schnell, Melanie},
title = {{A} systematic study of intermolecular interactions in
non-covalently bound complexes by using and expanding
advanced broadband rotational spectroscopy},
school = {University of Hamburg},
type = {Dissertation},
reportid = {PUBDB-2022-01316},
pages = {182},
year = {2020},
note = {Dissertation, University of Hamburg, 2020},
abstract = {The interplay between intra- and intermolecular forces,
with hydrogen bonding and London dispersion interactions
being among the most important ones, drives bio-molecular
aggregation and recognition processes. Although London
dispersion interactions were described in 1930 by Fritz
London, the importance of their contribution to intra- and
intermolecular interactions is still not well understood at
the quantitative level. With geometrically well‐defined
molecular model systems, where the interplay between
dispersion and hydrogen bonding is particularly interesting,
it is possible to systematically examine and quantify the
London dispersion contribution to intermolecular interaction
energies.The spectroscopy of the model systems in a cold
environment can give spectroscopic data of these systems at
low temperatures and isolated conditions, and this data can
be directly compared with the results from various
theoretical methods. Further, the experimental information
can be taken to benchmark quantum-chemical methods and can
be utilized in the development and the testing of newer
theoretical methods. Rotational spectroscopy, as employed in
this work, is a high resolution and highly sensitive
technique, which provides accurate structural information on
the different binding sites in the model systems and about
the intra- and intermolecular interactions within these
complexes.Within the framework of this thesis, three kinds
of complexes were studied in a systematic approach, which
can serve as suitable challenging systems for the
theoretical description and characterization of dispersion
interactions. The first explores the effect of dispersion
interactions when complexes are dominated by a strong
classical OH–O hydrogen bond, as studied in camphor
complexes with methanol and ethanol, respectively. In the
second category, the effect of dispersion interaction is
explored when complexes can form either via strong,
classical OH–O hydrogen bonds and weaker OH–π bonds in
the same molecule, as studied in the complexes of phenyl
vinyl ether with methanol, diphenyl ether with water,
tert-butyl alcohol and adamantanol, and dibenzofuran with
water, methanol, and tert-butyl alcohol. In the third
category, the effect of dispersion interaction on molecular
aggregation is investigated via complexes formed only by
weak OH–π and/or CH-O hydrogen bonds as well as π-π
dispersion interactions, as in the study of homodimers of
three similar molecules, diphenyl ether, dibenzofuran, and
fluorene, which have different structural flexibility.
Through these different model systems, we aim to investigate
how a preferred complex structure changes either by
introducing small changes in the main molecule or the
binding partner or on aggregation.The development of
chirped-pulse Fourier transform microwave spectroscopy has
enabled the recording of wide portions of a rotational
spectrum in a time-efficient way. With the advancement in
electronics, it is now possible to build microwave
spectrometers in a cost-effective way. Herein, a new design
of a cost-effective 18-26 GHz microwave spectrometer, based
on a segmented chirped-pulse approach, is built and
evaluated. This new design will help to make the powerful
technique of rotational spectroscopy more widespread.},
cin = {CFEL-SDCCM / FS-SMP},
cid = {I:(DE-H253)CFEL-SDCCM-20160915 /
I:(DE-H253)FS-SMP-20171124},
pnm = {631 - Matter – Dynamics, Mechanisms and Control
(POF4-631)},
pid = {G:(DE-HGF)POF4-631},
experiment = {EXP:(DE-MLZ)NOSPEC-20140101},
typ = {PUB:(DE-HGF)11},
urn = {urn:nbn:de:gbv:18-107163},
url = {https://bib-pubdb1.desy.de/record/475303},
}