Protons Relaxation and Temperature Dependence Due To Tunneling Methyl Group
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This research paper investigates the temperature dependence of proton spin-lattice relaxation time (T1) in samples containing tertiary-butyl groups, utilizing NMR techniques across a temperature range of 4-300K. The results indicate that the tunneling frequency and relaxation behavior of methyl groups are influenced by the molecular environment and potential barriers for reorientation, with some novel observations of tunneling in tert-butyl. Additionally, the study highlights the importance of collective motion of methyl groups and provides insights into the dynamics of molecular relaxation in solid-state systems.
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ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20
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Protons Relaxation and Temperature Dependence Due To Tunneling
Methyl Group
Yousif Abid Al-SHAABANI
Open Education College Iraq
ABSTRACT
Tunneling frequency and temperature dependence of proton spin lattice relaxation time T1, are depend upon the
height and the shape of the hindering barrier of methyl rotation and carry information on the group is molecular
environment are reported for some samples containing tertiary-butyl group.The temperature rang was 4-
300k.Data has been analyzed to provide estimates for the magnitude of the three fold potential barrier to
reorientation of all methyl groups in these materials. At low temperature the motion of the tertiary-butyl protons
can usually be neglected. All protons of the samples relax as a single system.In one or two cases tunneling is
observed for the first time in Tert-butyl. The T1 results are used to evaluate tunnel frequency in other cases. The
result suggest the importance of collective motion of methyl group in tert-butyl
I. INTRODUCTION
The methyl group has been used as the
ideal system for study of atomic and molecules
motion in the solid state. The reasons for the choice
have been discussed by a number of authors and for
example in review by press and reference [1].
The tunneling rotation of CH3 is usually
determined by the molecular environment of the
group which sets up potential barriers to the
rotation. Measurementof the CH3 tunnel splitting
barrier at low temperature provides us with
accurate values for the magnitude and the shape of
the potential barrier along with predictions for the
hierarch of torsional state within the barrier.
The latters have been approach of Clough
et al [2, 3]. Here the phenomenological model of
S.Stciskal and Gutowsky [4]has been modified and
the quantum mechanical principle formalized to
provide a single parameter theory in which the only
variable is the barriers height. This is in contrast to
theories which introduce.
Phonon interactions explicitly in which
many unknown coupling are invoked [5]. The
samples chose for this investigation are Tert-butyl
alcohol, 2,2 Dimethylpentanol, Tert methyl acetate,
Tert-Butyl nitrate and Tert-Butyl hypocloridare
included here as example of how the relaxation of
(CH3)3 changes, it is our aim to find the behavior of
tertiary butyl group when it is in contact with
different atoms.
In this work the temperature dependence
of proton spin lattice relaxation (T1) for all samples
studied in order to provide a further test of the
validity of Clough et al model. The (N.M.R)
technique was used to perform the experimental
measurement.
II. EXPERIMENTAL DETAILS
Measurement of the CH3 tunnel splitting
using dipole-dipole driven N.M.R experiment,
measurement of proton spin lattice relaxation T1,
were made on pulsed N.M.R, spectrometer system
which operates at 2l MHz.A saturation- recovery
technique was employed and recovered
magnetization was observed to grow exponentially
with experimental error. For T1 experiments the
temperature between room temperature and
4kcould be reached by pumping helium from the
bath surround the superconducting magnet into a
dewar, vessel running through its central bore. A
needle valve controlled the flow rate. A period of
sample preparation at high field (Typically 5T) was
made prior to each scan in a manner of techniques
describe to be Clough et al. [6, 7].
III. RESULT AND DISCUSSION
3-1 The low field measurement in tertary-butlyl
group sample.
The low field N.M.R data for this series
are shown from figure (1-5). Each one is aplotof
magnetic field in mT versus the magnetization is
arbitrary unity. A summary of the tunneling
frequency of these samples is shown is table (1).
From it one can see the barrier height and tunnel
frequency changes. These change in the barrier
heights and the tunnel frequencies are presumed to
be due to the different in crystal field from different
samples.
3-2 T1 versus Temperature
The T1 measurement will be presented
and compared with the predication of well-
established correlation between splitting of the
ground torsional state (ħ, t) and temperature at
RESEARCH ARTICLE OPEN ACCESS](https://image.slidesharecdn.com/c0604041720-160728112112/85/Protons-Relaxation-and-Temperature-Dependence-Due-To-Tunneling-Methyl-Group-1-320.jpg)
![Yousifabidal-SHAABANI. Int. Journal of Engineering Research and Applications www.ijera.com
ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20
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which T1 is a minimum and the well be connected
to the molecular environment of methyl group in
the unit cell.
Fig (1- 5) display the results of
measurement upon the samples in Fig (2). We
observed two minima. These are clearly observed
at 74.7 and 148.8 K. this is an interestingsample in
its relaxation behavior. The T1 at the minimum in
Fig (2) is small enough in indicate that almost all
the protons in sample are involved in the motion. In
some samples at a low temperature minimum
occurs due to a morewedlyhindered methyl group.
The data of Fig (2) is remarkable because
the t-butyl minimum is very shallow. The only
possible explanation for this that the t-butyl group
is already rotates as a whole at low temperature.
There by contributing to the low temperature
minimum when the methyl groups begin to rotate
within the t-butyl group. The dipole-dipole
interactionis already time dependent due to the
rotation of the t-butyl group at a whole cross
relaxation due to the dipolar interactions is still
much more rapid than spin-lattice relaxation [8].
Consequently all protons of the samples relax as a
single system. If all protons of a single molecule
are relaxed by a single methyl group, the relaxation
is slower than if the group were isolated see Fig (1)
and Fig (2).
IV. CONCLUSION
In this paper measurement of dependence
(T) of the protons spin lattice relaxation rate (T1) in
the Tert-Butyl Alcohol 2,2 Dimetylpentanol, Tert-
methyl acetate, Tert-Butyl nitrate and Tert-Butyl
hypoclorid at a Larmer frequency of W/2=21
MHz. These studies aidin the investigation of the
nature of molecular reorientation. The chosen our
experimental work in these samples to point out a
few interesting and important features of the
general problems of the proton spin-lattice
relaxation in molecules solid as the temperature are
varied.
The temperature of the T1 minimum are
quits similar to other CH3 group attached to
SP3
hydridised atoms. The value of T1 at the
minimum shows that in most cases rotation is fast
compared with rotation of the whole t-butyl group,
but the case of Tert-methyl acctate is anomalous.
We interpret the T1 minimum versus temperature
data with the theory. Clough et al. this is used to
estimate the tunnel frequency for the t-butyl series
and other samples.
REFERENCES
[1]. Press, W. (2005). Single-particle rotations
in molecular crystals (pp. 1-126). Springer
Berlin Heidelberg.
[2]. Clough, S., Heidemann, A., Horsewill, A.
J., Lewis, J. D., & Paley, M. N. J. (2009).
The correlation of methyl tunneling and
thermally activated reorientation. Journal
of Physics C: Solid State Physics, 14(19),
L525.
[3]. Clough, S., Heidemann, A., Horsewill, A.
J., Lewis, J. D., & Paley, M. N. J. (2012).
The rate of thermally activated methyl
group rotation in solids. Journal of
Physics C: Solid State Physics, 15(11),
2495.
[4]. Stejskal, E., O., and Gutowsky, H., S., J.
Chem. Phys., 388, 2013.
[5]. Hewson, A. C. (2011). The temperature
dependence of inelastic neutron scattering
in rotational tunneling systems. I.
Formulation and perturbation theory.
Journal of Physics C: Solid State Physics,
15(18), 3841.
[6]. Clough, S., A., Horsewirr, A., J., and
Madonald, P., J., J. Phys. C, 17,
1115,2013.
[7]. Vanhecke, P. and Janssens, G., PEV. B,
17, 2124, 2015.
[8]. Haupt, J. (2000). Einfluß von
quanteneffekten der methyl group
penrotation auf die kernrelaxation in
festkörpern. ZeitschriftfürNaturforschung
A, 26(10), 1578-1589.
Fig. 1 The temperature dependence of T1 in Tert-
butyl alcohol at NMR Frequency 21 MHz.](https://image.slidesharecdn.com/c0604041720-160728112112/85/Protons-Relaxation-and-Temperature-Dependence-Due-To-Tunneling-Methyl-Group-2-320.jpg)
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ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20
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Table 1.
Sample
Structure
Formula
Tmin[k]
νtHz
predicted
νtKHz
measured
V3[k]
Ea
[k]
Tert-butyl
alcohol
163 8104 170±2
127±2
1850 770
2,2,
Dimethylpent
anol
74.7
148.8
0.6107
0.5105
1100
2050
577
1211
Tert-methyl
acetate
114.3 1106
1600 1240
Tert-Butyl
nitrate
146.8 0.7105
2000 1180
Tert-Butyl
hypoclorid
165 8104
382±5
112±5
90±5
1780 480](https://image.slidesharecdn.com/c0604041720-160728112112/85/Protons-Relaxation-and-Temperature-Dependence-Due-To-Tunneling-Methyl-Group-4-320.jpg)
Protons Relaxation and Temperature Dependence Due To Tunneling Methyl Group
- 1. Yousifabidal-SHAABANI. Int. Journal of Engineering Research and Applications www.ijera.com ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20 www.ijera.com 17|P a g e Protons Relaxation and Temperature Dependence Due To Tunneling Methyl Group Yousif Abid Al-SHAABANI Open Education College Iraq ABSTRACT Tunneling frequency and temperature dependence of proton spin lattice relaxation time T1, are depend upon the height and the shape of the hindering barrier of methyl rotation and carry information on the group is molecular environment are reported for some samples containing tertiary-butyl group.The temperature rang was 4- 300k.Data has been analyzed to provide estimates for the magnitude of the three fold potential barrier to reorientation of all methyl groups in these materials. At low temperature the motion of the tertiary-butyl protons can usually be neglected. All protons of the samples relax as a single system.In one or two cases tunneling is observed for the first time in Tert-butyl. The T1 results are used to evaluate tunnel frequency in other cases. The result suggest the importance of collective motion of methyl group in tert-butyl I. INTRODUCTION The methyl group has been used as the ideal system for study of atomic and molecules motion in the solid state. The reasons for the choice have been discussed by a number of authors and for example in review by press and reference [1]. The tunneling rotation of CH3 is usually determined by the molecular environment of the group which sets up potential barriers to the rotation. Measurementof the CH3 tunnel splitting barrier at low temperature provides us with accurate values for the magnitude and the shape of the potential barrier along with predictions for the hierarch of torsional state within the barrier. The latters have been approach of Clough et al [2, 3]. Here the phenomenological model of S.Stciskal and Gutowsky [4]has been modified and the quantum mechanical principle formalized to provide a single parameter theory in which the only variable is the barriers height. This is in contrast to theories which introduce. Phonon interactions explicitly in which many unknown coupling are invoked [5]. The samples chose for this investigation are Tert-butyl alcohol, 2,2 Dimethylpentanol, Tert methyl acetate, Tert-Butyl nitrate and Tert-Butyl hypocloridare included here as example of how the relaxation of (CH3)3 changes, it is our aim to find the behavior of tertiary butyl group when it is in contact with different atoms. In this work the temperature dependence of proton spin lattice relaxation (T1) for all samples studied in order to provide a further test of the validity of Clough et al model. The (N.M.R) technique was used to perform the experimental measurement. II. EXPERIMENTAL DETAILS Measurement of the CH3 tunnel splitting using dipole-dipole driven N.M.R experiment, measurement of proton spin lattice relaxation T1, were made on pulsed N.M.R, spectrometer system which operates at 2l MHz.A saturation- recovery technique was employed and recovered magnetization was observed to grow exponentially with experimental error. For T1 experiments the temperature between room temperature and 4kcould be reached by pumping helium from the bath surround the superconducting magnet into a dewar, vessel running through its central bore. A needle valve controlled the flow rate. A period of sample preparation at high field (Typically 5T) was made prior to each scan in a manner of techniques describe to be Clough et al. [6, 7]. III. RESULT AND DISCUSSION 3-1 The low field measurement in tertary-butlyl group sample. The low field N.M.R data for this series are shown from figure (1-5). Each one is aplotof magnetic field in mT versus the magnetization is arbitrary unity. A summary of the tunneling frequency of these samples is shown is table (1). From it one can see the barrier height and tunnel frequency changes. These change in the barrier heights and the tunnel frequencies are presumed to be due to the different in crystal field from different samples. 3-2 T1 versus Temperature The T1 measurement will be presented and compared with the predication of well- established correlation between splitting of the ground torsional state (ħ, t) and temperature at RESEARCH ARTICLE OPEN ACCESS
- 2. Yousifabidal-SHAABANI. Int. Journal of Engineering Research and Applications www.ijera.com ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20 www.ijera.com 18|P a g e which T1 is a minimum and the well be connected to the molecular environment of methyl group in the unit cell. Fig (1- 5) display the results of measurement upon the samples in Fig (2). We observed two minima. These are clearly observed at 74.7 and 148.8 K. this is an interestingsample in its relaxation behavior. The T1 at the minimum in Fig (2) is small enough in indicate that almost all the protons in sample are involved in the motion. In some samples at a low temperature minimum occurs due to a morewedlyhindered methyl group. The data of Fig (2) is remarkable because the t-butyl minimum is very shallow. The only possible explanation for this that the t-butyl group is already rotates as a whole at low temperature. There by contributing to the low temperature minimum when the methyl groups begin to rotate within the t-butyl group. The dipole-dipole interactionis already time dependent due to the rotation of the t-butyl group at a whole cross relaxation due to the dipolar interactions is still much more rapid than spin-lattice relaxation [8]. Consequently all protons of the samples relax as a single system. If all protons of a single molecule are relaxed by a single methyl group, the relaxation is slower than if the group were isolated see Fig (1) and Fig (2). IV. CONCLUSION In this paper measurement of dependence (T) of the protons spin lattice relaxation rate (T1) in the Tert-Butyl Alcohol 2,2 Dimetylpentanol, Tert- methyl acetate, Tert-Butyl nitrate and Tert-Butyl hypoclorid at a Larmer frequency of W/2=21 MHz. These studies aidin the investigation of the nature of molecular reorientation. The chosen our experimental work in these samples to point out a few interesting and important features of the general problems of the proton spin-lattice relaxation in molecules solid as the temperature are varied. The temperature of the T1 minimum are quits similar to other CH3 group attached to SP3 hydridised atoms. The value of T1 at the minimum shows that in most cases rotation is fast compared with rotation of the whole t-butyl group, but the case of Tert-methyl acctate is anomalous. We interpret the T1 minimum versus temperature data with the theory. Clough et al. this is used to estimate the tunnel frequency for the t-butyl series and other samples. REFERENCES [1]. Press, W. (2005). Single-particle rotations in molecular crystals (pp. 1-126). Springer Berlin Heidelberg. [2]. Clough, S., Heidemann, A., Horsewill, A. J., Lewis, J. D., & Paley, M. N. J. (2009). The correlation of methyl tunneling and thermally activated reorientation. Journal of Physics C: Solid State Physics, 14(19), L525. [3]. Clough, S., Heidemann, A., Horsewill, A. J., Lewis, J. D., & Paley, M. N. J. (2012). The rate of thermally activated methyl group rotation in solids. Journal of Physics C: Solid State Physics, 15(11), 2495. [4]. Stejskal, E., O., and Gutowsky, H., S., J. Chem. Phys., 388, 2013. [5]. Hewson, A. C. (2011). The temperature dependence of inelastic neutron scattering in rotational tunneling systems. I. Formulation and perturbation theory. Journal of Physics C: Solid State Physics, 15(18), 3841. [6]. Clough, S., A., Horsewirr, A., J., and Madonald, P., J., J. Phys. C, 17, 1115,2013. [7]. Vanhecke, P. and Janssens, G., PEV. B, 17, 2124, 2015. [8]. Haupt, J. (2000). Einfluß von quanteneffekten der methyl group penrotation auf die kernrelaxation in festkörpern. ZeitschriftfürNaturforschung A, 26(10), 1578-1589. Fig. 1 The temperature dependence of T1 in Tert- butyl alcohol at NMR Frequency 21 MHz.
- 3. Yousifabidal-SHAABANI. Int. Journal of Engineering Research and Applications www.ijera.com ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20 www.ijera.com 19|P a g e Fig. 2The temperature dependence of T1 in 2,2, Dimethyl pentanol at NMR Frequency 21 MHz. Fig. 3 The temperature dependence of T1 in Tert- methyl acetate at NMR frequency 21 MHz. Fig. 4 The temperature dependence of T1 in tert- butyl -nitrite at NMR Frequency 21 MHz. Fig. 5: The low field NMR spectra (4k) of Tert- Butyl hypoclorid recoded at a veriety of frequency. See text for details.
- 4. Yousifabidal-SHAABANI. Int. Journal of Engineering Research and Applications www.ijera.com ISSN: 2248-9622, Vol. 6, Issue 4, (Part - 4) April 2016, pp.17-20 www.ijera.com 20|P a g e Table 1. Sample Structure Formula Tmin[k] νtHz predicted νtKHz measured V3[k] Ea [k] Tert-butyl alcohol 163 8104 170±2 127±2 1850 770 2,2, Dimethylpent anol 74.7 148.8 0.6107 0.5105 1100 2050 577 1211 Tert-methyl acetate 114.3 1106 1600 1240 Tert-Butyl nitrate 146.8 0.7105 2000 1180 Tert-Butyl hypoclorid 165 8104 382±5 112±5 90±5 1780 480