XIV
h
International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
118
T9: O–2
DFT calculations on (1H-1,2,4-triazol-3-ylsulfanyl)acetic acid
Justyna Sienkiewicz-Gromiuk
1
1
Department of General and Coordination Chemistry, Maria Curie-Sklodowska University,
M. Curie-Sklodowska Sq. 2, 20-031 Lublin, Poland,
e-mail: j.sienkiewicz-gromiuk@poczta.umcs.lublin.pl
Compounds containing 1,2,4-triazole moiety and ring system are widely used in chemistry,
biology, medicine and agriculture because they exhibit a broad spectrum of biological properties
such as antifungal, antibacterial, antimicrobial, anticancer, analgesic, antitumor, antitubercular,
herbicidal, anticonvulsant and anti-inflamatory [1, 2]. 1,2,4,-triazole and its derivatives are used
as a versatile reagent in the synthesis of many heterocycles. Furthermore, 1,2,4-triazole
derivatives can coordinate to metal ions in different ways depending upon the donor sites of the
ligand [3].
The molecule of (1H-1,2,4-triazol-3-ylsulfanyl)acetic acid (Fig. 1A) consists of a 1,2,4-
triazole nucleus and a flexible aliphatic thioacetic (−SCH
2
COOH) chain. The determined crystal
structure of (1H-1,2,4-triazol-3-ylsulfanyl)acetic acid (Fig. 1B) confirms that three kinds of
donor atoms are involved in creating a network of intermolecular hydrogen bonds, including
N−H···O, O−H···N and N−H···S interactions whose function is to stabilize the two-dimensional
wave-like layered supramolecular architecture existing in the solid state [4].
The ground state geometric structure together with the vibrational and electronic features of
(1H-1,2,4-triazol-3-ylsulfanyl)acetic was identified using molecular spectroscopic techniques
and DFT studies. The calculations of various molecular properties for the optimized geometry
such as the dipole moment, Mulliken atomic charges, frontier molecular orbital energies, global
reactivity descriptors, molecular electrostatic potential (MEP) and electrostatic potential (ESP)
surfaces were also performed. In order to test the effect of hydrogen bonding on the vibrational
wavenumbers, the calculations for the hydrogen bonded model containing the N−H···O,
O−H···N and N−H···S interactions similar to those existing in a crystal were also made
Fig. 1. (A) Molecular structure of (1H-1,2,4-triazol-3-ylsulfanyl)acetic acid;
(B) Part of the crystal structure of the acid showing the network of intermolecular hydrogen bonds.
Keywords: (1H-1,2,4-triazol-3-ylsulfanyl)acetic acid; DFT computations; vibrational spectroscopy
References
[1] Z.H. Chohan, S.H. Sumrra, M.H. Youssoufi, T.B. Hadda, Eur. J. Med. Chem. 45 (2010) 2739.
[2] L. Mazur, A.E. Kozioł, B. Modzelewska-Banachewicz, Acta Cryst. E60 (2004) 2244.
[3] Z.H. Chohan, S.H. Sumrra, J. Enzyme Inhib. Med. Chem. 25 (2010) 599.
[4] Y.-T. Wang, R.-S. Xin, J.-G. Wang, Z. Kristallogr. NCS 225 (2010) 751.
XIV
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International Conference on Molecular Spectroscopy, Białka Tatrzańska 2017
119
T9: O–3
Water tetrahedron intercalated with hydronium ion (H
3
O
+
)
as molecular reactor producing deuterium under X-ray absorption:
New insight
Alexander Udal'tsov
1
1
Faculty of Biology, Lomonosov Moscow State University, Vorobjovy Gory 12, 119234 Moscow,
Russia, e-mail: avu151@yandex.ru
Features of X-ray absorption and emission spectra of H
2
O and D
2
O have been interpreted in
terms of polaronic exciton theory under interaction with the incident photon [1]. Further details
of kinetic energy accumulation by polaronic exciton system depicted in Fig. 1 under Compton
interaction, when fifteen-step of Compton wavelength (15λ
C
/2π) is required to obtain polaronic
exciton radius providing kinetic energy 534.556 eV, and deuterium creation are reported in the
present work. The polaronic exciton theory admits to evaluate the energy levels taking into
account inelastic effects for water tetrahedron intercalated with H
3
O
+
.
Fig. 1. Plot of Larmor frequency relatively to angular frequency (ω
L
/ω
t
) of electronic polaron coupled with
shared proton versus the distance (r
ex,0
– r
ex,n
)per the reduced Compton wavelength units, where r
ex,0
= 0.385325 Å,
and r
ex,n
= r
ex,0
– n λ
C
/(2π); and illustration of Larmor precession of the electronic polaron emerging due to
electromagnetic field generated by the incident photon; spiral line shows electron pathway along the orbits, while
transition between the orbits happens by a hopping step of n λ
C
/(2π), on the right. Proton sharing with the central
water molecule is shown above.
Consideration of the precessing polaronic exciton in the magnetic field generated by the
incident electromagnetic wave under Compton interaction admits to derive the following
formula for electromagnetic mass of neutrino (m
ν
) via electromagnetic mass of electron using
Larmor precession frequency related to angular frequency of electron (ω
L
/ω
t
), which shows up a
correlation with Compton interaction steps.
m
ν
=[e
2
α
/(3π
2
ε
0
λ
C
c
2
)](2m
e
ef
/m
h
ef
)
(1)
where m
h
ef
and m
e
ef
are respectively the effective masses of hole and electronic polarons, e and α
are the elementary charge (e = 1.6021765×10
–19
C) and fine structure constant, ε
0
and c are
electric constant (ε
0
=0.88541878×10
–11
F m
–1
) and the speed of light, respectively. With
m
h
ef
=9.51m
e
and m
e
ef
=0.5m
e
assumed for condensed matter [2], where m
e
is the electron mass,
the calculated neutrino mass m
ν
=3.445467×10
–37
kg.
Keywords: polaronic exciton; compton wavelength; neutrino
References
[1] A.V. Udal'tsov, J. Mol. Liquid. (2017), submitted after revision.
[2] A.V. Udal'tsov, J. Mol. Struct. 1125 (2016) 522.
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