Orientador: Roy Edward Bruns / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-08T20:57:48Z (GMT). No. of bitstreams: 1 Cesar_PauloHenrique_M.pdf: 1005998 bytes, checksum: a962e8dd40f25da4750c20492dd58820 (MD5) Previous issue date: 2007 / Resumo: A Teoria Quântica de Átomos em Moléculas (QTAIM) é utilizada para decompor as derivadas do momento dipolar e as intensidades de infravermelho das moléculas AB3 (A=N, P; B=H, F) em contribuições de carga¿fluxo de carga-fluxo de dipolo (CCFDF). Os cálculos realizados no nível MP2/6-311++G(3d,3p) obteve valores das intensidades de infravermelho com as cargas e dipolos atômicos QTAIM que diferem em 13,8 km mol dos valores experimentais não considerando as vibrações de estiramento das moléculas de NH3 e PH3, em que ocorrem sobreposição das bandas experimentais. Os dipolos atômicos dos átomos de nitrogênio e fósforo são muito importantes na determinação do momento dipolar das moléculas de NF3, PH3 e PF3, enquanto que as cargas atômicas são quase totalmente responsáveis pelo momento dipolar da molécula de NH3. O fluxo de dipolo do átomo central é mais importante na determinação das intensidades das bandas de estiramento de todas as moléculas, enquanto contribui muito pouco para as intensidades das bandas de deformação. As contribuições dos fluxos de dipolos dos átomos terminais devem ser consideradas para descrever com maior precisão as intensidades de todas as moléculas. A expectativa que se tem com o modelo momento de ligação simples, é do domínio da contribuição de carga para as derivadas do momento de dipolo e intensidades das moléculas NH3, NF3 e PF3. Entretanto, as contribuições de fluxo de carga e fluxo de dipolo são muito grandes para todas as vibrações do PH3, cancelando-se no modo de estiramento e reforçando-se nos modos de deformação. / Abstract: The quantum theory of atoms in molecules (QTAIM) has been used to decompose dipole moment derivatives and fundamental infrared intensities of the AB3 (A=N, P; B=H, F) molecules into charge-charge flux-dipole flux (CCFDF) contributions. Calculations were carried out at the MP2/6-311++G(3d,3p) level. Infrared intensities calculated from the QTAIM atomic charges and atomic dipoles are within 13.8 km mol of the experimental values not considering the NH3 and PH3 stretching vibrations for which the experimental bands are severely overlapped. Group V atomic dipoles are very important in determining the molecular dipole moments of NF3, PH3 and PF3 although the atomic charges account for almost all the NH3 molecular moment. Dipole fluxes on the Group V atom are important in determining the stretching band intensities of all molecules whereas they make small contributions to the bending mode intensities. Consideration of dipole flux contributions from the terminal atoms must also be made for accurately describing the intensities of all these molecules. As expected from a simple bond moment model, charge contributions dominate for most of the NH3, NF3 and PF3 dipole moment derivatives and intensities. Charge flux and dipole flux contributions are very substantial for all the PH3 vibrations, canceling each other for the stretching modes and reinforcing one another for the bending modes. / Mestrado / Físico-Química / Mestre em Química

A study of procedures and techniques of measuring dielectric constant and dipole moment of liquids.

The dielectric constant or relative static permittivity of a material represents the capacitance of the material relative to a vacuum and is important in many industrial applications. Nevertheless, accurate experimental values are often unavailable and current prediction methods lack accuracy and are often unreliable. A new QSPR (quantitative structure-property relation) correlation of dielectric constant for pure organic chemicals is developed and tested. The average absolute percent error is expected to be less than 3% when applied to hydrocarbons and non-polar compounds and less than 18% when applied to polar compounds with dielectric constant values ranging from 1.0 to 50.0. A local composition model is developed for mixture dielectric constants based on the Nonrandom-Two-Liquid (NRTL) model commonly used for correlating activity coefficients in vapor-liquid equilibrium data regression. It is predictive in that no mixture dielectric constant data are used and there are no adjustable parameters. Predictions made on 16 binary and six ternary systems at various compositions and temperatures compare favorably to extant correlations data that require experimental values to fit an adjustable parameter in the mixing rule and are significantly improved over values predicted by Oster's equation that also has no adjustable parameters. In addition, molecular dynamics (MD) simulations provide an alternative to analytic relations. Results suggest that MD simulations require very accurate force field models, particularly with respect to the charge distribution within the molecules, to yield accurate pure chemical values of dielectric constant, but with the development of more accurate pure chemical force fields, it appears that mixture simulations of any number of components are likely possible. Using MD simulations, the impact of different portions of the force field on the calculated dielectric constant were examined. The results obtained suggest that rotational polarization arising from the permanent dipole moments makes the dominant contribution to dielectric constant. Changes in the dipole moment due to angle bending and bond stretching (distortion polarization) have less impact on dielectric constant than rotational polarization due to permanent dipole alignment, with angle bending being more significant than bond stretching.

To accurately solve the general nuclear spin state function in Nuclear Magnetic Resonance (NMR), a rotation wave approach was employed, allowing the reference frame to rotate in sync with the oscillating magnetic field. The spin state system was analogously treated as a Rubik's Cube, ensuring the diagonalization of only the time-dependent part of the state function. Although Gottfried's equation (1966) aligns with transitions between specific spin states m and m′, his second rotation contradicts the conservation of angular momentum, resulting in inaccuracies for spin states with initial phase shifts or entangled states. Contrarily, Schwinger (1937) efficiently computed the coefficients for each spin state in a frequency range opposite to the Larmor frequency, using an unorthodox approach in quantum mechanics, which unfortunately led to the oversight of his work in subsequent citations. This methodology was also applied to derive the general electron spin state function in Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR), enabling the construction of a doubly rotated ground state for time-dependent perturbation theory. This was particularly relevant as the Hamiltonians for magnetic dipole, electric quadrupole, and magnetic octupole moments incorporate powers of I · J terms, necessitating the calculation of sub-state energy levels for perturbation, including those of molecules 14N7 and 7Li3. Furthermore, the study expanded to the general Lie group for 3D rotations along three linearly independent axes, resulting in 12 distinct methods to achieve rotations in any arbitrary direction using these axes, yielding wave function with only one spin operator in each exponent. The ongoing research is now concentrated on generating NMR spectra for 14N7 in amino acids, furthering the understanding of nuclear spin dynamics in complex molecular systems.

We give a brief introduction to atomic physics and the motivation behind our experiments in the first chapter. The electron’s electric dipole moment is an interesting quantity which is yet to be measured. In the 3rd Chapter, we use the technique of chopped non-linear magneto-optic rotation (NMOR) in a room temperature Cs vapor cell to measure the permanent electric dipole moment (EDM) in the atom. The cell has paraffin coating on the walls to increase the relaxation time. The signature of the EDM is a shift in the Larmor precession frequency correlated with the application of an E field. We analyze errors in the technique, and show that the main source of systematic error is the appearance of a longitudinal magnetic field when an electric field is applied. This error can be eliminated by doing measurements on the two ground hyperfine levels. Using an E field of 2.6 kV/cm, we place an upper limit on the electron EDM of 2.9 × 10−22 e-cm with 95% confidence. This limit can be increased by 7 orders-of-magnitude—and brought below the current best experimental value. We give future directions for how this may be achieved. In chapter 4, we examine the Hanle effect for linear and circularly polarized light for different ground states and we find opposite behavior in the transmission signal. In one case, it shifts from enhanced transmission to enhanced absorption and vice-versa in the other case. In Chapter 5, we study the transmission spectrum at different temperatures and device a way to find the number density. We then verify the Clausius-Clapeyron equation and also find the latent heat of vaporization of Cs. Finally, we wrap up with conclusions and future directions.

A new neutron Electric Dipole Moment (nEDM) experiment was proposed to be commissioned at the Fundamental Neutron Physics Beamline at the Spallation Neutron Source (SNS) of the Oak Ridge National Laboratory (ORNL). The underlying theme of this experiment (first conceived by Golub and Lamoreaux in 1994) is the search for new physics beyond the Standard Model of particle physics. The discovery of a non-zero nEDM would be of revolutionary importance to physics, with the discovery of such providing for evidence for new-beyond-the-Standard-Model physics required for a resolution to the unresolved puzzle of why the universe is dominated by matter, as opposed to anti-matter. A first demonstration of a new magnetic field monitoring system for a neutron electric dipole moment experiment is presented. The system is designed to reconstruct the vector components of the magnetic field in the interior measurement region solely from exterior measurements. The results highlight the potential for the implementation of an improved system in an upcoming neutron electric dipole moment experiment to be carried out at the Spallation Neutron Source at Oak Ridge National Laboratory.

Probing orientations of fluorescent molecules embedded in or attached to cell membranes has a great potential to reveal information on membrane structure and processes occurring in living cells. In this thesis, we first describe one- and two-photon linear dichroism measurements on a fluorescent probe embedded in a phospholipid membrane with a well- defined lipid composition. On the basis of experimental data, we determine the distribution of the angle between the one-photon transition dipole moment of the probe and the membrane normal. At the same time, we perform molecular dynamics simulations of the fluorescent probe and quantum calculations of its one-photon and two-photon absorption properties. By comparing the orientational distribution gained from experiments with that predicted by simulations, we test the ability of linear dichroism measurements to report on the orientation of a fluorescent molecule in a lipid membrane. We also examine the applicability of molecular simulations as a basis for the interpretation of experimental data.

<p>In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules.</p><p>A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state.</p><p>By means of the DC Stark effect, permanent electric dipole moments of HfS in the <i>D</i> ¹Π state and HfO in the <i>b</i> ³Π₁ state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived.</p><p>The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS <i>D</i>¹Π and HfO<i> b</i> ³Π₁ states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output.</p><p>Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na₂ and Li₂.</p><p>A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na₂. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect.</p><p>Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.</p>

In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules. A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state. By means of the DC Stark effect, permanent electric dipole moments of HfS in the D 1Π state and HfO in the b 3Π1 state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived. The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS D 1Π and HfO b 3Π1 states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output. Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na2 and Li2. A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na2. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect. Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.

Rotationally averaged polarizabilities and intrinsic electric dipole moments of sodium clusters are measured and reported. The experimental method is a molecular beam deflection. Our precision is the highest (<5%) and the range of the cluster sizes is the broadest to date (Na₁₀ ∼ Na₃₀₀). Compared to the earlier measurements, our data covers all sizes with no gaps up to the largest cluster. The fine structure in the polarizability curve is previously unobserved. We have carefully ruled out several possible explanations. And we find an earlier existing theory could explain the facts but will lead to magic numbers which were not seen in some previous experiments. A detailed theory is needed to understand the behaviors we see. Intrinsic electric dipole moments (EDM) of sodium clusters are probed to answer the intriguing question: Do metal clusters develop electric dipole moments like molecules? Some theories have predicted the existence of EDM in ground state sodium clusters and gave their magnitudes. We put upper bounds on the EDM of sodium clusters and find that they are orders of magnitude smaller than the predictions. This provokes an interesting question: how can one define metallicity in metal clusters? Our measurements are performed at cryogenic temperature 20 Kelvin. At this temperature the clusters are believed to be in their vibronic ground states.