Toward spectroscopically accurate global ab initio potential energy surface for the acetylene-vinylidene isomerization

Science.gov (United States)

Han, Huixian; Li, Anyang; Guo, Hua

2014-12-01

A new full-dimensional global potential energy surface (PES) for the acetylene-vinylidene isomerization on the ground (S0) electronic state has been constructed by fitting ˜37 000 high-level ab initio points using the permutation invariant polynomial-neural network method with a root mean square error of 9.54 cm-1. The geometries and harmonic vibrational frequencies of acetylene, vinylidene, and all other stationary points (two distinct transition states and one secondary minimum in between) have been determined on this PES. Furthermore, acetylene vibrational energy levels have been calculated using the Lanczos algorithm with an exact (J = 0) Hamiltonian. The vibrational energies up to 12 700 cm-1 above the zero-point energy are in excellent agreement with the experimentally derived effective Hamiltonians, suggesting that the PES is approaching spectroscopic accuracy. In addition, analyses of the wavefunctions confirm the experimentally observed emergence of the local bending and counter-rotational modes in the highly excited bending vibrational states. The reproduction of the experimentally derived effective Hamiltonians for highly excited bending states signals the coming of age for the ab initio based PES, which can now be trusted for studying the isomerization reaction.

High-Pressure Catalytic Reactions of C6 Hydrocarbons on PlatinumSingle-Crystals and nanoparticles: A Sum Frequency Generation VibrationalSpectroscopic and Kinetic Study

Energy Technology Data Exchange (ETDEWEB)

Bratlie, Kaitlin [Univ. of California, Berkeley, CA (United States)

2007-01-01

Catalytic reactions of cyclohexene, benzene, n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene on platinum catalysts were monitored in situ via sum frequency generation (SFG) vibrational spectroscopy and gas chromatography (GC). SFG is a surface specific vibrational spectroscopic tool capable of monitoring submonolayer coverages under reaction conditions without gas-phase interference. SFG was used to identify the surface intermediates present during catalytic processes on Pt(111) and Pt(100) single-crystals and on cubic and cuboctahedra Pt nanoparticles in the Torr pressure regime and at high temperatures (300K-450K). At low pressures (<10^-6 Torr), cyclohexene hydrogenated and dehydrogenates to form cyclohexyl (C₆H₁₁) and π-allyl C₆H₉, respectively, on Pt(100). Increasing pressures to 1.5 Torr form cyclohexyl, π-allyl C₆H₉, and 1,4-cyclohexadiene, illustrating the necessity to investigate catalytic reactions at high-pressures. Simultaneously, GC was used to acquire turnover rates that were correlated to reactive intermediates observed spectroscopically. Benzene hydrogenation on Pt(111) and Pt(100) illustrated structure sensitivity via both vibrational spectroscopy and kinetics. Both cyclohexane and cyclohexene were produced on Pt(111), while only cyclohexane was formed on Pt(100). Additionally, π-allyl c-C₆H₉ was found only on Pt(100), indicating that cyclohexene rapidly dehydrogenates on the (100) surface. The structure insensitive production of cyclohexane was found to exhibit a compensation effect and was analyzed using the selective energy transfer (SET) model. The SET model suggests that the Pt-H system donates energy to the E_2u mode of free benzene, which leads to catalysis. Linear C₆ (n-hexane, 2-methylpentane, 3-methylpentane, and 1-hexene) hydrocarbons were also investigated in the presence and absence of excess hydrogen on Pt

THE POSSIBLE INTERSTELLAR ANION CH2CN–: SPECTROSCOPIC CONSTANTS, VIBRATIONAL FREQUENCIES, AND OTHER CONSIDERATIONS

International Nuclear Information System (INIS)

Fortenberry, Ryan C.; Lee, Timothy J.; Crawford, T. Daniel

2013-01-01

The A 1 B 1 ⇽ X-tilde 1 A' excitation into the dipole-bound state of the cyanomethyl anion (CH 2 CN – ) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X-tilde 1 A' CH 2 CN – in order to assist in laboratory studies and astronomical observations.

The Possible Interstellar Anion CH2CN-: Spectroscopic Constants, Vibrational Frequencies, and Other Considerations

Science.gov (United States)

Fortenberry, Ryan C.; Crawford, T. Daniel; Lee, Timothy J.

2013-01-01

The A\\ ^1B_1 \\leftarrow \\tilde{X}\\ ^1A^{\\prime } excitation into the dipole-bound state of the cyanomethyl anion (CH2CN-) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for \\tilde{X}\\ ^1A^{\\prime } CH2CN- in order to assist in laboratory studies and astronomical observations.

Raman spectroscopic study of some chalcopyrite-xanthate flotation products

CSIR Research Space (South Africa)

Andreev, GN

2003-12-16

Full Text Available of normal vibrations of the corresponding individual compounds. The latter facilitated the Raman spectroscopic elucidation of the reaction products formed on the chalcopyrite surface in real industrial flotation conditions with a sodium isopropyl xanthate...

Vibrational spectroscopic investigation of polymorphs and cocrystals of indomethacin.

Science.gov (United States)

Ali, Hassan Refat H; Alhalaweh, Amjad; Velaga, Sitaram P

2013-05-01

Identification of optimal solid form of an active pharmaceutical ingredient and form control are very important in drug development. Thus, the structural information of these forms and in-depth insight on the modes of molecular interactions are necessary, and vibrational spectroscopic methods are well suited for this purpose. In-depth structural analysis of different solid forms of indomethacin (IND) using Raman and infrared (IR) spectroscopy is the objective. We have investigated the modes of molecular interactions in polymorphs (α and γ), amorphous and discovered cocrystals of IND with nicotinamide (NIC) and trans-cinnamic acid (CIN) coformers. The solid forms of IND have been prepared; their purity has been verified by differential scanning calorimetry and powder X-ray diffractometry and then studied in the solid-state by Raman and IR spectroscopy. The modes of the interactions were closely investigated from the vibrational data. The key vibrational features of IND solid forms have been specified. The IR (C=O) band at 1713 cm(-1) attributed to cyclic acid dimer of γ IND has disappeared in IND-NIC/CIN whilst retained in IND-SAC cocrystal. IND cocrystallizes in different conformations and crystal lattices with different coformers. The cyclic acid dimer of IND has been kept on its cocrystallization with saccharin and it could have been broken with NIC and CIN. The complementary nature of Raman and IR spectroscopy allowed unambiguous investigation of the chemical composition of pharmaceutical materials which is of particular importance in the absence of detailed structural information, as in the case of IND-NIC and IND-CIN.

In situ study of nitrobenzene grafting on Si(111)-H surfaces by infrared spectroscopic ellipsometry

Energy Technology Data Exchange (ETDEWEB)

Rappich, J. [Helmholtz-Zentrum Berlin fuer Materialien und Energie GmbH, Institut fuer Silizium-Photovoltaik, Kekulestr. 5, 12489 Berlin (Germany); Hinrichs, K. [ISAS - Institute for Analytical Sciences, Department Berlin, Albert-Einstein-Str. 9, 12489 Berlin (Germany)

2009-12-15

The binding of nitrobenzene (NB) molecules from a solution of 4-nitrobenzene-diazonium-tetrafluoroborate on a Si(111)-H surface was investigated during the electrochemical processing in diluted sulphuric acid by means of infrared spectroscopic ellipsometry (IR-SE). The grafting was monitored by an increase in specific IR absorption bands due to symmetric and anti-symmetric NO{sub 2} stretching vibrations in the 1400-1700 cm{sup -1} regime. The p- and s-polarized reflectances were recorded within 20 s for each spectrum only. NB molecules were detected when bonded to the Si(111) surface but not in the 2 mM solution itself. Oxide formation on the NB grafted Si surface was observed after drying in inert atmosphere and not during the grafting process in the aqueous solution. (author)

Spectroscopic investigation of the vibrational quasi-continuum arising from internal rotation of a methyl group

Energy Technology Data Exchange (ETDEWEB)

Hougen, J.T. [NIST, Gaithersburg, MD (United States)

1993-12-01

The goal of this project is to use spectroscopic techniques to investigate in detail phenomena involving the vibrational quasi-continuum in a simple physical system. Acetaldehyde was chosen for the study because: (i) methyl groups have been suggested to be important promotors of intramolecular vibrational relaxation, (ii) the internal rotation of a methyl group is an easily describle large-amplitude motion, which should retain its simple character even at high levels of excitation, and (iii) the aldehyde carbonyl group offers the possibility of both vibrational and electronic probing. The present investigation of the ground electronic state has three parts: (1) understanding the {open_quotes}isolated{close_quotes} internal-rotation motion below, at, and above the top of the torsional barrier, (2) understanding in detail traditional (bond stretching and bending) vibrational fundamental and overtone states, and (3) understanding interactions involving states with multiquantum excitations of at least one of these two kinds of motion.

Spectroscopic parameters, vibrational levels, transition dipole moments and transition probabilities of the 9 low-lying states of the NCl+ cation

Science.gov (United States)

Yin, Yuan; Shi, Deheng; Sun, Jinfeng; Zhu, Zunlue

2018-03-01

This work calculates the potential energy curves of 9 Λ-S and 28 Ω states of the NCl+ cation. The technique employed is the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson correction. The Λ-S states are X2Π, 12Σ+, 14Π, 14Σ+, 14Σ-, 24Π, 14Δ, 16Σ+, and 16Π, which are yielded from the first two dissociation channels of NCl+ cation. The Ω states are generated from these Λ-S states. The 14Π, 14Δ, 16Σ+, and 16Π states are inverted with the spin-orbit coupling effect included. The 14Σ+, 16Σ+, and 16Π states are very weakly bound, whose well depths are only several-hundred cm- 1. One avoided crossing of PECs occurs between the 12Σ+ and 22Σ+ states. To improve the quality of potential energy curves, core-valence correlation and scalar relativistic corrections are included. The potential energies are extrapolated to the complete basis set limit. The spectroscopic parameters and vibrational levels are calculated. The transition dipole moments are computed. The Franck-Condon factors, Einstein coefficients, and radiative lifetimes of many transitions are determined. The spectroscopic approaches are proposed for observing these states according to the transition probabilities. The spin-orbit coupling effect on the spectroscopic and vibrational properties is evaluated. The spectroscopic parameters, vibrational levels, transition dipole moments, as well as transition probabilities reported in this paper could be considered to be very reliable.

Two-Photon Vibrational Spectroscopy using local optical fields of gold and silver nanostructures

Science.gov (United States)

Kneipp, Katrin; Kneipp, Janina; Kneipp, Harald

2007-03-01

Spectroscopic effects can be strongly affected when they take place in the immediate vicinity of metal nanostructures due to coupling to surface plasmons. We introduce a new approach that suggests highly efficient two-photon labels as well as two-photon vibrational spectroscopy for non-destructive chemical probing. The underlying spectroscopic effect is the incoherent inelastic scattering of two photons on the vibrational quantum states performed in the enhanced local optical fields of gold nanoparticles, surface enhanced hyper Raman scattering (SEHRS). We infer effective two-photon cross sections for SEHRS on the order of 10^5 GM, similar or higher than the best known cross sections for two-photon fluorescence. SEHRS combines the advantages of two-photon spectroscopy with the structural information of vibrational spectroscopy, and the high sensitivity and nanometer-scale local confinement of plasmonics-based spectroscopy.

High throughput assessment of cells and tissues: Bayesian classification of spectral metrics from infrared vibrational spectroscopic imaging data.

Science.gov (United States)

Bhargava, Rohit; Fernandez, Daniel C; Hewitt, Stephen M; Levin, Ira W

2006-07-01

Vibrational spectroscopy allows a visualization of tissue constituents based on intrinsic chemical composition and provides a potential route to obtaining diagnostic markers of diseases. Characterizations utilizing infrared vibrational spectroscopy, in particular, are conventionally low throughput in data acquisition, generally lacking in spatial resolution with the resulting data requiring intensive numerical computations to extract information. These factors impair the ability of infrared spectroscopic measurements to represent accurately the spatial heterogeneity in tissue, to incorporate robustly the diversity introduced by patient cohorts or preparative artifacts and to validate developed protocols in large population studies. In this manuscript, we demonstrate a combination of Fourier transform infrared (FTIR) spectroscopic imaging, tissue microarrays (TMAs) and fast numerical analysis as a paradigm for the rapid analysis, development and validation of high throughput spectroscopic characterization protocols. We provide an extended description of the data treatment algorithm and a discussion of various factors that may influence decision-making using this approach. Finally, a number of prostate tissue biopsies, arranged in an array modality, are employed to examine the efficacy of this approach in histologic recognition of epithelial cell polarization in patients displaying a variety of normal, malignant and hyperplastic conditions. An index of epithelial cell polarization, derived from a combined spectral and morphological analysis, is determined to be a potentially useful diagnostic marker.

Sum frequency generation for surface vibrational spectroscopy

International Nuclear Information System (INIS)

Hunt, J.H.; Guyot-Sionnest, P.; Shen, Y.R.

1987-01-01

Surface vibrational spectroscopy is one of the best means for characterizing molecular adsorbates. For this reason, many techniques have been developed in the past. However, most of them suffer from poor sensitivity, low spectral and temporal resolution, and applications limited to vacuum solid interfaces. Recently, the second harmonic generation (SHG) technique was proved repeatedly to be a simple but versatile surface probe. It is highly sensitive and surface specific; it is also capable of achieving high temporal, spatial, and spectral resolution. Being an optical technique, it can be applied to any interface accessible by light. The only serious drawback is its lack of molecular selectivity. An obvious remedy is the extension of the technique to IR-visible sum frequency generation (SFG). Surface vibrational spectroscopy with submonolayer sensitivity is then possible using SFG with the help of a tunable IR laser. The authors report here an SFG measurement of the C-H stretch vibration of monolayers of molecules at air-solid and air-liquid interfaces

System Ba/sub 2/Znsub(1-x)Cusub(x)UO/sub 6/ - a vibrational spectroscopic proof of the Jahn Teller effect

Energy Technology Data Exchange (ETDEWEB)

Kemmler-Sack, S; Rother, H J [Tuebingen Univ. (Germany, F.R.). Inst. fuer Chemie

1979-01-01

The ordered perovskites Ba/sub 2/ZnUO/sub 6/ (cubic, space group Fm3m) and Ba/sub 2/CuUO/sub 6/ (tetragonal, space group I/sub 4//mmm) form solid solutions. For small Cu content the lattice symmetry is cubic, with x>=0.25 an increasing tetragonal distortion (c/a ..sqrt..2 > 1) is observed. From the vibrational spectra and in accordance with the factor group analysis the symmetry of the UO/sub 6/ octahedra is for small Cu content Osub(h) and on the Cu-rich side Dsub(4h). In the region of the lattice vibrations (T/sub 2/ field) the lifting of the degeneracy - due to the Jahn Teller effect of Cu/sup 2 +/ - leads to a band separation, which decreases with sinking copper content. Therefore the Jahn Teller effect is easily noticeable with vibrational spectroscopic methods. In the corresponding series with Wsup(VI) the vibrational spectroscopic investigations lead qualitatively to the same results as in the Usup(VI) system. As further examples the stacking polytypes Ba/sub 2/ZnTeO/sub 6/ and Ba/sub 2/CuTeO/sub 6/ are considered. The vibrational spectra show, that the Jahn Teller effect in this lattice, which is strengthened by partial face-sharing of octahedra, is less pronounced than in the perovskites in which only corner-sharing is present.

Recent advances in the applications of vibrational spectroscopic imaging and mapping to pharmaceutical formulations

Science.gov (United States)

Ewing, Andrew V.; Kazarian, Sergei G.

2018-05-01

Vibrational spectroscopic imaging and mapping approaches have continued in their development and applications for the analysis of pharmaceutical formulations. Obtaining spatially resolved chemical information about the distribution of different components within pharmaceutical formulations is integral for improving the understanding and quality of final drug products. This review aims to summarise some key advances of these technologies over recent years, primarily since 2010. An overview of FTIR, NIR, terahertz spectroscopic imaging and Raman mapping will be presented to give a perspective of the current state-of-the-art of these techniques for studying pharmaceutical samples. This will include their application to reveal spatial information of components that reveals molecular insight of polymorphic or structural changes, behaviour of formulations during dissolution experiments, uniformity of materials and detection of counterfeit products. Furthermore, new advancements will be presented that demonstrate the continuing novel applications of spectroscopic imaging and mapping, namely in FTIR spectroscopy, for studies of microfluidic devices. Whilst much of the recently developed work has been reported by academic groups, examples of the potential impacts of utilising these imaging and mapping technologies to support industrial applications have also been reviewed.

Vibrational Spectroscopy and Astrobiology

Science.gov (United States)

Chaban, Galina M.; Kwak, D. (Technical Monitor)

2001-01-01

Role of vibrational spectroscopy in solving problems related to astrobiology will be discussed. Vibrational (infrared) spectroscopy is a very sensitive tool for identifying molecules. Theoretical approach used in this work is based on direct computation of anharmonic vibrational frequencies and intensities from electronic structure codes. One of the applications of this computational technique is possible identification of biological building blocks (amino acids, small peptides, DNA bases) in the interstellar medium (ISM). Identifying small biological molecules in the ISM is very important from the point of view of origin of life. Hybrid (quantum mechanics/molecular mechanics) theoretical techniques will be discussed that may allow to obtain accurate vibrational spectra of biomolecular building blocks and to create a database of spectroscopic signatures that can assist observations of these molecules in space. Another application of the direct computational spectroscopy technique is to help to design and analyze experimental observations of ice surfaces of one of the Jupiter's moons, Europa, that possibly contains hydrated salts. The presence of hydrated salts on the surface can be an indication of a subsurface ocean and the possible existence of life forms inhabiting such an ocean.

Structural and vibrational studies of clean and chemisorbed metal surfaces

International Nuclear Information System (INIS)

Jiang, Qing-Tang.

1992-01-01

Using Medium Energy Ion Scattering, we have studied the structural and vibrational properties of a number of clean and chemisorbed metal surfaces. The work presented in this thesis is mainly of a fundamental nature. However, it is believed that an atomistic understanding of the forces that affect surface structural and vibrational properties can have a beneficial impact on a large number of areas of applied nature. We find that the surface structure of Cu(001) follows the common trend for metal surfaces, where a small oscillatory relaxation exists beginning with a slight contraction in the top layer. In addition, the surface vibrational amplitude is enhanced (as s usually the case) by ∼80%. A detailed analysis of our data shows an unexpected anisotropy of the vibrational amplitude, such that the out-of-plane vibrational amplitude is 30% smaller than the in-plane vibrational amplitude. The unexpected results may imply a large tensile stress on Cu(001). Upon adsorption of 1/4 of a monolayer of S, a p(2 x 2)-S/Cu(001) surface is created. This submonolayer amount of S atoms makes the surface bulk-like, in which the anisotropy of the surface vibrations is removed and the first interlayer contraction is lifted. By comparing our model to earlier contradictory results on this controversial system. We find excellent agreement with a recent LEED study. The presence of 0.1 monolayer of Ca atoms on the Au(113) surface induces a drastic atomic rearrangements, in which half of the top layer Au atoms are missing and a (1 x 2) symmetry results. In addition, the first interlayer spacing of Au(113) is significantly reduced. Our results are discussed in terms of the energy balance between competing surface electronic charge densities

THE POSSIBLE INTERSTELLAR ANION CH{sub 2}CN{sup -}: SPECTROSCOPIC CONSTANTS, VIBRATIONAL FREQUENCIES, AND OTHER CONSIDERATIONS

Energy Technology Data Exchange (ETDEWEB)

Fortenberry, Ryan C.; Lee, Timothy J. [NASA Ames Research Center, Moffett Field, CA 94035-1000 (United States); Crawford, T. Daniel, E-mail: Ryan.C.Fortenberry@nasa.gov, E-mail: Timothy.J.Lee@nasa.gov [Department of Chemistry, Virginia Tech, Blacksburg, VA 24061 (United States)

2013-01-10

The A {sup 1}B{sub 1} Leftwards-Open-Headed-Arrow X-tilde{sup 1}A' excitation into the dipole-bound state of the cyanomethyl anion (CH{sub 2}CN{sup -}) has been hypothesized as the carrier for one diffuse interstellar band. However, this particular molecular system has not been detected in the interstellar medium even though the related cyanomethyl radical and the isoelectronic ketenimine molecule have been found. In this study, we are employing the use of proven quartic force fields and second-order vibrational perturbation theory to compute accurate spectroscopic constants and fundamental vibrational frequencies for X-tilde{sup 1} A' CH{sub 2}CN{sup -} in order to assist in laboratory studies and astronomical observations.

Characterization of polymer surface structure and surface mechanical behaviour by sum frequency generation surface vibrational spectroscopy and atomic force microscopy

International Nuclear Information System (INIS)

Opdahl, Aric; Koffas, Telly S; Amitay-Sadovsky, Ella; Kim, Joonyeong; Somorjai, Gabor A

2004-01-01

Sum frequency generation (SFG) vibrational spectroscopy and atomic force microscopy (AFM) have been used to study polymer surface structure and surface mechanical behaviour, specifically to study the relationships between the surface properties of polymers and their bulk compositions and the environment to which the polymer is exposed. The combination of SFG surface vibrational spectroscopy and AFM has been used to study surface segregation behaviour of polyolefin blends at the polymer/air and polymer/solid interfaces. SFG surface vibrational spectroscopy and AFM experiments have also been performed to characterize the properties of polymer/liquid and polymer/polymer interfaces, focusing on hydrogel materials. A method was developed to study the surface properties of hydrogel contact lens materials at various hydration conditions. Finally, the effect of mechanical stretching on the surface composition and surface mechanical behaviour of phase-separated polyurethanes, used in biomedical implant devices, has been studied by both SFG surface vibrational spectroscopy and AFM. (topical review)

Laser method of acoustical emission control from vibrating surfaces

Science.gov (United States)

Motyka, Zbigniew

2013-01-01

For limitation of the noise in environment, the necessity occurs of determining and location of sources of sounds emitted from surfaces of many machines and devices, assuring in effect the possibility of suitable constructional changes implementation, targeted at decreasing of their nuisance. In the paper, the results of tests and calculations are presented for plane surface sources emitting acoustic waves. The tests were realized with the use of scanning laser vibrometer which enabled remote registration and the spectral analysis of the surfaces vibrations. The known hybrid digital method developed for determination of sound wave emission from such surfaces divided into small finite elements was slightly modified by distinguishing the phase correlations between such vibrating elements. The final method being developed may find use in wide range of applications for different forms of vibrations of plane surfaces.

Vibrational and chiroptical spectroscopic characterization of gamma-turn model cyclic tetrapeptides containing two beta-Ala residues.

Science.gov (United States)

Vass, Elemér; Majer, Zsuzsa; Kohalmy, Krisztina; Hollósi, Miklós

2010-08-01

The optical spectroscopic characterization of gamma-turns in solution is uncertain and their distinction from beta-turns is often difficult. This work reports systematic ECD and vibrational circular dichroism (VCD) spectroscopic studies on gamma-turn model cyclic tetrapeptides cyclo(Ala-beta-Ala-Pro-beta-Ala) (1), cyclo(Pro-beta-Ala-Pro-beta-Ala) (2) and cyclo(Ala-beta-Ala-Ala-beta-Ala) (3). Conformational analysis performed at the 6-31G(d)/B3LYP level of theory using an adequate PCM solvent model predicted one predominant conformer for 1-3, featuring two inverse gamma-turns. The ECD spectra in ACN of 1 and 2 are characterized by a negative n-->pi* band near 230 nm and a positive pi-->pi* band below 200 nm with a long wavelength shoulder. The ECD spectra in TFE of 1-3 show similar spectra with blue-shifted bands. The VCD spectra in ACN-d(3) of 1 and 2 show a +/-/+/- amide I sign pattern resulting from four uncoupled vibrations in the case of 1 and a sequence of two positive couplets in the case of 2. A -/+/+/- amide I VCD pattern was measured for 3 in TFE-d(2). All three peptides give a positive couplet or couplet-like feature (+/-) in the amide II region. VCD spectroscopy, in agreement with theoretical calculations revealed that low frequency amide I vibrations (at approximately 1630 cm(-1) or below) are indicative of a C(7) H-bonded inverse gamma-turns with Pro in position 2, while gamma-turns encompassing Ala absorb at higher frequency (above 1645 cm(-1)). Copyright 2010 Wiley-Liss, Inc.

Application for vibration monitoring of aspheric surface machining based on wireless sensor networks

Science.gov (United States)

Han, Chun Guang; Guo, Yin Biao; Jiang, Chen

2010-05-01

Any kinds of tiny vibration of machine tool parts will have a great influence on surface quality of the workpiece at ultra-precise machining process of aspheric surface. At present the major way for decreasing influence of vibration is machining compensation technology. Therefore it is important for machining compensation control to acquire and transmit these vibration signals effectively. This paper presents a vibration monitoring system of aspheric surface machining machine tool based on wireless sensor networks (WSN). Some key issues of wireless sensor networks for vibration monitoring system of aspheric surface machining are discussed. The reliability of data transmission, network communication protocol and synchronization mechanism of wireless sensor networks are studied for the vibration monitoring system. The proposed system achieves multi-sensors vibration monitoring involving the grinding wheel, the workpiece and the workbench spindle. The wireless transmission of vibration signals is achieved by the combination with vibration sensor nodes and wireless network. In this paper, these vibration sensor nodes are developed. An experimental platform is structured which employs wireless sensor networks to the vibration monitoring system in order to test acquisition and wireless transmission of vibration signal. The test results show that the proposed system can achieve vibration data transmission effectively and reliability and meet the monitoring requirements of aspheric surface machining machine tool.

Minimization of Surface Roughness and Tool Vibration in CNC Milling Operation

Directory of Open Access Journals (Sweden)

Sukhdev S. Bhogal

2015-01-01

Full Text Available Tool vibration and surface roughness are two important parameters which affect the quality of the component and tool life which indirectly affect the component cost. In this paper, the effect of cutting parameters on tool vibration, and surface roughness has been investigated during end milling of EN-31 tool steel. Response surface methodology (RSM has been used to develop mathematical model for predicting surface finish, tool vibration and tool wear with different combinations of cutting parameters. The experimental results show that feed rate is the most dominating parameter affecting surface finish, whereas cutting speed is the major factor effecting tool vibration. The results of mathematical model are in agreement with experimental investigations done to validate the mathematical model.

Molecular structure, vibrational spectroscopic analysis (IR & Raman), HOMO-LUMO and NBO analysis of anti-cancer drug sunitinib using DFT method

Science.gov (United States)

Mıhçıokur, Özlem; Özpozan, Talat

2017-12-01

Oxindole and its derivatives have wide applications in different industries such as in synthetic & natural fibers, dyes for hair and plastic materials in addition to their biological importance. In the present study, one of the oxindole derivatives, N-(2-diethylaminoethyl)-5-[(Z)-(5-fluoro-2-oxo-1H-indol-3-ylidene)methyl]-2,4-dimethyl-1H-pyrrole-3-carboxamide (Sunitinib), which is used as an anti-cancer drug, was investigated in terms of structural, vibrational spectroscopic and theoretical analysis. The calculations have been performed for gaseous, aqueous and DMSO phases, respectively. Potential Energy Surface (PES) scan has been carrried out to obtain the most stable structures of all the phases of the title molecule using B3LYP/6-31G(d,p) level and the geometrical variations among them are discussed. The solvent effect for Sunitinib in aqueous and DMSO phases have been performed by means of the self-consistent recognition reaction field (SCRF) method as implemented in the integral equation formalism polarized continuum model (IEFPCM). On the other hand, NBO analysis has been carried out to understand probable hydrogen bonding sites and charge transfers. Additionally, the HOMO and the LUMO energies are calculated using B3LYP/6-31G(d,p) to determine the intra molecular charge transfers (ICT) within the molecule and the kinetic stabilities for each phases. The molecular electrostatic potential surface (MESP) has been plotted over the optimized structure to estimate the reactive sites of electrophilic and nucleophilic attacks regarding Sunitinib molecule. The potential energy distribution (PED) has been calculated using VEDA4 program and vibrational assignments of the experimental spectra (IR & Raman) have been elucidated by means of the calculated vibrational spectra. The observed vibrational spectra of Sunitinib is compared with the calculated spectra obtained by using B3LYP functional both with 6-31G(d,p) and 6-311++G(d,p) basis sets. Theoretical results

Vibration of Piezoelectric Nanowires Including Surface Effects

Directory of Open Access Journals (Sweden)

R. Ansari

2014-04-01

Full Text Available In this paper, surface and piezoelectric effects on the vibration behavior of nanowires (NWs are investigated by using a Timoshenko beam model. The electric field equations and the governing equations of motion for the piezoelectric NWs are derived with the consideration of surface effects. By the exact solution of the governing equations, an expression for the natural frequencies of NWs with simply-supported boundary conditions is obtained. The effects of piezoelectricity and surface effects on the vibrational behavior of Timoshenko NWs are graphically illustrated. A comparison is also made between the predictions of Timoshenko beam model and those of its Euler-Bernoulli counterpart. Additionally, the present results are validated through comparison with the available data in the literature.

Spectroscopic Studies of Molecular Systems relevant in Astrobiology

Science.gov (United States)

Fornaro, Teresa

2016-01-01

In the Astrobiology context, the study of the physico-chemical interactions involving "building blocks of life" in plausible prebiotic and space-like conditions is fundamental to shed light on the processes that led to emergence of life on Earth as well as to molecular chemical evolution in space. In this PhD Thesis, such issues have been addressed both experimentally and computationally by employing vibrational spectroscopy, which has shown to be an effective tool to investigate the variety of intermolecular interactions that play a key role in self-assembling mechanisms of nucleic acid components and their binding to mineral surfaces. In particular, in order to dissect the contributions of the different interactions to the overall spectroscopic signals and shed light on the intricate experimental data, feasible computational protocols have been developed for the characterization of the spectroscopic properties of such complex systems. This study has been carried out through a multi-step strategy, starting the investigation from the spectroscopic properties of the isolated nucleobases, then studying the perturbation induced by the interaction with another molecule (molecular dimers), towards condensed phases like the molecular solid, up to the case of nucleic acid components adsorbed on minerals. A proper modeling of these weakly bound molecular systems has required, firstly, a validation of dispersion-corrected Density Functional Theory methods for simulating anharmonic vibrational properties. The isolated nucleobases and some of their dimers have been used as benchmark set for identifying a general, reliable and effective computational procedure based on fully anharmonic quantum mechanical computations of the vibrational wavenumbers and infrared intensities within the generalized second order vibrational perturbation theory (GVPT2) approach, combined with the cost-effective dispersion-corrected density functional B3LYP-D3, in conjunction with basis sets of

Vibrational effects on surface energies and band gaps in hexagonal and cubic ice

International Nuclear Information System (INIS)

Engel, Edgar A.; Needs, Richard J.; Monserrat, Bartomeu

2016-01-01

Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range from −1.2 eV for the cubic ice basal surface up to −1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice.

Infrared spectroscopic and voltammetric study of adsorbed CO on stepped surfaces of copper monocrystalline electrodes

International Nuclear Information System (INIS)

Koga, O.; Teruya, S.; Matsuda, K.; Minami, M.; Hoshi, N.; Hori, Y.

2005-01-01

Voltammetric and infrared (IR) spectroscopic measurements were carried out to study adsorbed CO on two series of copper single crystal electrodes n(111)-(111) and n(111)-(100) in 0.1M KH 2 PO 4 +0.1M K 2 HPO 4 at 0 o C. Reversible voltammetric waves were observed below -0.55V versus SHE for adsorption of CO which displaces preadsorbed phosphate anions. The electric charge of the redox waves is proportional to the step atom density for both single crystal series. This fact indicates that phosphate anions are specifically adsorbed on the step sites below -0.55V versus SHE. Voltammetric measurements indicated that (111) terrace of Cu is covered with adsorbed CO below -0.5V versus SHE. Nevertheless, no IR absorption band of adsorbed CO is detected from (111) terrace. Presence of adsorbed CO on (111) terrace is presumed which is not visible by the potential difference spectroscopy used in the present work. IR spectroscopic measurements showed that CO is reversibly adsorbed with an on-top manner on copper single crystal electrodes of n(111)-(111) and n(111)-(100) with approximately same wavenumber of C?O stretching vibration of 2070cm -1 . The IR band intensity is proportional to the step atom density. Thus CO is adsorbed on (111) or (100) steps on the single crystal surfaces. An analysis of the IR band intensity suggested that one CO molecule is adsorbed on every two or more Cu step atom of the monocrystalline surface. The spectroscopic data were compared with those reported for uhv system. The C-O stretching wavenumber of adsorbed CO in the electrode-electrolyte system is 30-40cm -1 lower than those in uhv system

Internal reflection spectroscopic analysis of sulphide mineral surfaces

International Nuclear Information System (INIS)

Kaoma, J.

1989-01-01

To establish the reason for flotation of sulfide minerals in the absence of any conventional collector, internal reflection spectroscopic analysis (IRS) of their surfaces was conducted. sulfur, sulfates, thiosulfates, and hydrocarbonates have been detected on the surface of as-grand sulfide minerals. On sodium sulfide-treated surfaces, both sulfur and polysulfide have also been found to be present. From these findings, the flotation of sulfide minerals without collectors is discussed. (author). 26 refs

Vibrational and electronic spectroscopic studies of melatonin

Science.gov (United States)

Singh, Gurpreet; Abbas, J. M.; Dogra, Sukh Dev; Sachdeva, Ritika; Rai, Bimal; Tripathi, S. K.; Prakash, Satya; Sathe, Vasant; Saini, G. S. S.

2014-01-01

We report the infrared absorption and Raman spectra of melatonin recorded with 488 and 632.8 nm excitations in 3600-2700 and 1700-70 cm-1 regions. Further, we optimized molecular structure of the three conformers of melatonin within density functional theory calculations. Vibrational frequencies of all three conformers have also been calculated. Observed vibrational bands have been assigned to different vibrational motions of the molecules on the basis of potential energy distribution calculations and calculated vibrational frequencies. Observed band positions match well with the calculated values after scaling except Nsbnd H stretching mode frequencies. It is found that the observed and calculated frequencies mismatch of Nsbnd H stretching is due to intermolecular interactions between melatonin molecules.

Observation of the adsorption and desorption of vibrationally excited molecules on a metal surface

Science.gov (United States)

Shirhatti, Pranav R.; Rahinov, Igor; Golibrzuch, Kai; Werdecker, Jörn; Geweke, Jan; Altschäffel, Jan; Kumar, Sumit; Auerbach, Daniel J.; Bartels, Christof; Wodtke, Alec M.

2018-06-01

The most common mechanism of catalytic surface chemistry is that of Langmuir and Hinshelwood (LH). In the LH mechanism, reactants adsorb, become thermalized with the surface, and subsequently react. The measured vibrational (relaxation) lifetimes of molecules adsorbed at metal surfaces are in the range of a few picoseconds. As a consequence, vibrational promotion of LH chemistry is rarely observed, with the exception of LH reactions occurring via a molecular physisorbed intermediate. Here, we directly detect adsorption and subsequent desorption of vibrationally excited CO molecules from a Au(111) surface. Our results show that CO (v = 1) survives on a Au(111) surface for 1 × 10-10 s. Such long vibrational lifetimes for adsorbates on metal surfaces are unexpected and pose an interesting challenge to the current understanding of vibrational energy dissipation on metal surfaces. They also suggest that vibrational promotion of surface chemistry might be more common than is generally believed.

A Simple Surface-Enhanced Raman Spectroscopic Method for on-Site Screening of Tetracycline Residue in Whole Milk

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Sagar Dhakal

2018-02-01

Full Text Available Therapeutic and subtherapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain tetracycline residue. This study developed a simple surface-enhanced Raman spectroscopic (SERS method for on-site screening of tetracycline residue in milk and water. Six batches of silver colloid nanoparticles were prepared for surface enhancement measurement. Milk-tetracycline and water-tetracycline solutions were prepared at seven concentration levels (1000, 500, 100, 10, 1, 0.1, and 0.01 ppm and spiked with silver colloid nanoparticles. A 785 nm Raman spectroscopic system was used for spectral measurement. Tetracycline vibrational modes were observed at 1285, 1317 and 1632 cm−1 in water-tetracycline solutions and 1322 and 1621 cm−1 (shifted from 1317 and 1632 cm−1, respectively in milk-tetracycline solutions. Tetracycline residue concentration as low as 0.01 ppm was detected in both the solutions. The peak intensities at 1285 and 1322 cm−1 were used to estimate the tetracycline concentrations in water and milk with correlation coefficients of 0.92 for water and 0.88 for milk. Results indicate that this SERS method is a potential tool that can be used on-site at field production for qualitative and quantitative detection of tetracycline residues.

A Simple Surface-Enhanced Raman Spectroscopic Method for on-Site Screening of Tetracycline Residue in Whole Milk.

Science.gov (United States)

Dhakal, Sagar; Chao, Kuanglin; Huang, Qing; Kim, Moon; Schmidt, Walter; Qin, Jianwei; Broadhurst, C Leigh

2018-02-01

Therapeutic and subtherapeutic use of veterinary drugs has increased the risk of residue contamination in animal food products. Antibiotics such as tetracycline are used for mastitis treatment of lactating cows. Milk expressed from treated cows before the withdrawal period has elapsed may contain tetracycline residue. This study developed a simple surface-enhanced Raman spectroscopic (SERS) method for on-site screening of tetracycline residue in milk and water. Six batches of silver colloid nanoparticles were prepared for surface enhancement measurement. Milk-tetracycline and water-tetracycline solutions were prepared at seven concentration levels (1000, 500, 100, 10, 1, 0.1, and 0.01 ppm) and spiked with silver colloid nanoparticles. A 785 nm Raman spectroscopic system was used for spectral measurement. Tetracycline vibrational modes were observed at 1285, 1317 and 1632 cm -1 in water-tetracycline solutions and 1322 and 1621 cm -1 (shifted from 1317 and 1632 cm -1 , respectively) in milk-tetracycline solutions. Tetracycline residue concentration as low as 0.01 ppm was detected in both the solutions. The peak intensities at 1285 and 1322 cm -1 were used to estimate the tetracycline concentrations in water and milk with correlation coefficients of 0.92 for water and 0.88 for milk. Results indicate that this SERS method is a potential tool that can be used on-site at field production for qualitative and quantitative detection of tetracycline residues.

Spectroscopic investigation of oxidized solder surfaces

International Nuclear Information System (INIS)

Song, Jenn-Ming; Chang-Chien, Yu-Chien; Huang, Bo-Chang; Chen, Wei-Ting; Shie, Chi-Rung; Hsu, Chuang-Yao

2011-01-01

Highlights: → UV-visible spectroscopy is successfully used to evaluate the degree of discoloring of solders. → The surface oxides of solders can also be identified by UV-visible absorption spectra. → The discoloration of solder surface can be correlated with optical characterization of oxides. → A strategy against discoloring by alloying was also suggested. - Abstract: For further understanding of the discoloration of solder surfaces due to oxidation during the assembly and operation of electronic devices, UV-vis and X-ray photoelectron spectroscopic analyses were applied to evaluate the degree of discoloring and identify the surface oxides. The decrease in reflectance of the oxidized solder surface is related to SnO whose absorption band is located within the visible region. A trace of P can effectively depress the discoloration of solders under both solid and semi-solid states through the suppression of SnO.

Surface hopping simulation of vibrational predissociation of methanol dimer

Science.gov (United States)

Jiang, Ruomu; Sibert, Edwin L.

2012-06-01

The mixed quantum-classical surface hopping method is applied to the vibrational predissociation of methanol dimer, and the results are compared to more exact quantum calculations. Utilizing the vibrational SCF basis, the predissociation problem is cast into a curve crossing problem between dissociative and quasibound surfaces with different vibrational character. The varied features of the dissociative surfaces, arising from the large amplitude OH torsion, generate rich predissociation dynamics. The fewest switches surface hopping algorithm of Tully [J. Chem. Phys. 93, 1061 (1990), 10.1063/1.459170] is applied to both diabatic and adiabatic representations. The comparison affords new insight into the criterion for selecting the suitable representation. The adiabatic method's difficulty with low energy trajectories is highlighted. In the normal crossing case, the diabatic calculations yield good results, albeit showing its limitation in situations where tunneling is important. The quadratic scaling of the rates on coupling strength is confirmed. An interesting resonance behavior is identified and is dealt with using a simple decoherence scheme. For low lying dissociative surfaces that do not cross the quasibound surface, the diabatic method tends to overestimate the predissociation rate whereas the adiabatic method is qualitatively correct. Analysis reveals the major culprits involve Rabi-like oscillation, treatment of classically forbidden hops, and overcoherence. Improvements of the surface hopping results are achieved by adopting a few changes to the original surface hopping algorithms.

Vibrational spectroscopic and quantum theoretical study of host-guest interactions in clathrates: I. Hofmann type clathrates

Directory of Open Access Journals (Sweden)

VLADIMIR M. PETRUSEVSKI

2000-06-01

Full Text Available Hofmann type clatharates are host-guest compounds with the general formula M(NH32M'(CN4·2G, in which M(NH32M'(CN4 is the host lattice and G is benzene, the guest molecule. In previous studies, host-guest interactions have been investigated by analyzing the RT and LNT vibrational (infrared, far infrared and Raman spectra of these clathrates. All the observed changes in the vibrational spectra of these clathrates are referred to a host-guest interaction originating from weak hydrogen bonding between the ammonia hydrogen atoms from the host lattice and the p electron cloud of the guest (benzene molecules. In order to obtain an insight into the relative importance of the local crystalline field vs. the anharmonicity effects on the spectroscopic properties of the guest species upon enclathration, as well as to explain the observed band shifts and splittings, several quantum theoretical approaches are proposed.

Vibrations of alkali metal overlayers on metal surfaces

International Nuclear Information System (INIS)

Rusina, G G; Eremeev, S V; Borisova, S D; Echenique, P M; Chulkov, E V; Benedek, G

2008-01-01

We review the current progress in the understanding of vibrations of alkalis adsorbed on metal surfaces. The analysis of alkali vibrations was made on the basis of available theoretical and experimental results. We also include in this discussion our recent calculations of vibrations in K/Pt(111) and Li(Na)/Cu(001) systems. The dependence of alkali adlayer localized modes on atomic mass, adsorption position and coverage as well as the dependence of vertical vibration frequency on the substrate orientation is discussed. The square root of atomic mass dependence of the vertical vibration energy has been confirmed by using computational data for alkalis on the Al(111) and Cu(001) substrates. We have confirmed that in a wide range of submonolayer coverages the stretch mode energy remains nearly constant while the energy of in-plane polarized modes increases with the increase of alkali coverage. It was shown that the spectrum of both stretch and in-plane vibrations can be very sensitive to the adsorption position of alkali atoms and substrate orientation

DIAGNOSTICS OF WORKPIECE SURFACE CONDITION BASED ON CUTTING TOOL VIBRATIONS DURING MACHINING

Directory of Open Access Journals (Sweden)

Jerzy Józwik

2015-05-01

Full Text Available The paper presents functional relationships between surface geometry parameters, feed and vibrations level in the radial direction of the workpiece. Time characteristics of the acceleration of cutting tool vibration registered during C45 steel and stainless steel machining for separate axes (X, Y, Z were presented as a function of feedrate f. During the tests surface geometric accuracy assessment was performed and 3D surface roughness parameters were determined. The Sz parameter was selected for the analysis, which was then collated with RMS vibration acceleration and feedrate f. The Sz parameter indirectly provides information on peak to valley height and is characterised by high generalising potential i.e. it is highly correlated to other surface and volume parameters of surface roughness. Test results presented in this paper may constitute a valuable source of information considering the influence of vibrations on geometric accuracy of elements for engineers designing technological processes.

Surface vibrational modes in disk-shaped resonators.

Science.gov (United States)

Dmitriev, A V; Gritsenko, D S; Mitrofanov, V P

2014-03-01

The natural frequencies and distributions of displacement components for the surface vibrational modes in thin isotropic elastic disks are calculated. In particular, the research is focused on even solutions for low-lying resonant vibrations with large angular wave numbers. Several families of modes are found which are interpreted as modified surface modes of an infinitely long cylinder and Lamb modes of a plate. The results of calculation are compared with the results of the experimental measurements of vibrational modes generated by means of resonant excitation in duraluminum disk with radius of ≈90 mm and thickness of 16 mm in the frequency range of 130-200 kHz. An excellent agreement between the calculated and measured frequencies is found. Measurements of the structure of the resonant peaks show splitting of some modes. About a half of the measured modes has splitting Δfsplit/fmode at the level of the order of 10(-5). The Q-factors of all modes measured in vacuum lie in the interval (2…3)×10(5). This value is typical for duraluminum mechanical resonators in the ultrasonic frequency range. Copyright © 2013 Elsevier B.V. All rights reserved.

Expansion Hamiltonian model for a diatomic molecule adsorbed on a surface: Vibrational states of the CO/Cu(100) system including surface vibrations

Energy Technology Data Exchange (ETDEWEB)

Meng, Qingyong, E-mail: mengqingyong@dicp.ac.cn [State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, 116023 Dalian (China); Meyer, Hans-Dieter, E-mail: hans-dieter.meyer@pci.uni-heidelberg.de [Theoretische Chemie, Physikalisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg (Germany)

2015-10-28

Molecular-surface studies are often done by assuming a corrugated, static (i.e., rigid) surface. To be able to investigate the effects that vibrations of surface atoms may have on spectra and cross sections, an expansion Hamiltonian model is proposed on the basis of the recently reported [R. Marquardt et al., J. Chem. Phys. 132, 074108 (2010)] SAP potential energy surface (PES), which was built for the CO/Cu(100) system with a rigid surface. In contrast to other molecule-surface coupling models, such as the modified surface oscillator model, the coupling between the adsorbed molecule and the surface atoms is already included in the present expansion SAP-PES model, in which a Taylor expansion around the equilibrium positions of the surface atoms is performed. To test the quality of the Taylor expansion, a direct model, that is avoiding the expansion, is also studied. The latter, however, requests that there is only one movable surface atom included. On the basis of the present expansion and direct models, the effects of a moving top copper atom (the one to which CO is bound) on the energy levels of a bound CO/Cu(100) system are studied. For this purpose, the multiconfiguration time-dependent Hartree calculations are carried out to obtain the vibrational fundamentals and overtones of the CO/Cu(100) system including a movable top copper atom. In order to interpret the results, a simple model consisting of two coupled harmonic oscillators is introduced. From these calculations, the vibrational levels of the CO/Cu(100) system as function of the frequency of the top copper atom are discussed.

Localized Surface Plasmons in Vibrating Graphene Nanodisks

DEFF Research Database (Denmark)

Wang, Weihua; Li, Bo-Hong; Stassen, Erik

2016-01-01

in graphene disks have the additional benefit to be highly tunable via electrical stimulation. Mechanical vibrations create structural deformations in ways where the excitation of localized surface plasmons can be strongly modulated. We show that the spectral shift in such a scenario is determined...... by a complex interplay between the symmetry and shape of the modal vibrations and the plasmonic mode pattern. Tuning confined modes of light in graphene via acoustic excitations, paves new avenues in shaping the sensitivity of plasmonic detectors, and in the enhancement of the interaction with optical emitters...

Nonplanar property study of antifungal agent tolnaftate-spectroscopic approach

Science.gov (United States)

Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.

2011-09-01

Vibrational analysis of the thionocarbamate fungicide tolnaftate which is antidermatophytic, antitrichophytic and antimycotic agent, primarily inhibits the ergosterol biosynthesis in the fungus, was carried out using NIR FT-Raman and FTIR spectroscopic techniques. The equilibrium geometry, various bonding features, harmonic vibrational wavenumbers and torsional potential energy surface (PES) scan studies have been computed using density functional theory method. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA.4 program. Vibrational spectra, natural bonding orbital (NBO) analysis and optimized molecular structure show the clear evidence for electronic interaction of thionocarbamate group with aromatic ring. Predicted electronic absorption spectrum from TD-DFT calculation has been compared with the UV-vis spectrum. The Mulliken population analysis on atomic charges and the HOMO-LUMO energy were also calculated. Vibrational analysis reveals that the simultaneous IR and Raman activation of the C-C stretching mode in the phenyl and naphthalene ring provide evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity as a fungicide.

Vibrational spectroscopic study of terbutaline hemisulphate

Science.gov (United States)

Ali, H. R. H.; Edwards, H. G. M.; Kendrick, J.; Scowen, I. J.

2009-05-01

The Raman spectrum of terbutaline hemisulphate is reported for the first time, and molecular assignments are proposed on the basis of ab initio BLYP DFT calculations with a 6-31G* basis set and vibrational frequencies predicted within the quasi-harmonic approximation; these predictions compare favourably with the observed vibrational spectra. Comparison with previously published infrared data explains several spectral features. The results from this study provide data that can be used for the preparative process monitoring of terbutaline hemisulphate, an important β 2 agonist drug in various dosage forms and its interaction with excipients and other components.

Nonlinear free vibration of piezoelectric nanobeams incorporating surface effects

International Nuclear Information System (INIS)

Hosseini-Hashemi, Shahrokh; Nahas, Iman; Fakher, Mahmood; Nazemnezhad, Reza

2014-01-01

In this study, the nonlinear free vibration of piezoelectric nanobeams incorporating surface effects (surface elasticity, surface tension, and surface density) is studied. The governing equation of the piezoelectric nanobeam is derived within the framework of Euler–Bernoulli beam theory with the von Kármán geometric nonlinearity. In order to satisfy the balance conditions between the nanobeam bulk and its surfaces, the component of the bulk stress, σ zz , is assumed to vary linearly through the nanobeam thickness. An exact solution is obtained for the natural frequencies of a simply supported piezoelectric nanobeam in terms of the Jacobi elliptic functions using the free vibration mode shape of the corresponding linear problem. Then, the influences of the surface effects and the piezoelectric field on the nonlinear free vibration of nanobeams made of aluminum and silicon with positive and negative surface elasticity, respectively, have been studied for various properties of the piezoelectric field, various nanobeam sizes and amplitude ratios. It is observed that if the Young’s modulus of a nanobeam is lower, the effect of the piezoelectric field on the frequency ratios (FRs) of the nanobeam will be greater. In addition, it is seen that by increasing the nanobeam length so that the nanobeam cross section is set to be constant, the surface effects and the piezoelectric field with negative voltage values increases the FRs, whereas it is the other way around when the nanobeam cross section is assumed to be dependent on the length of the nanobeam. (paper)

The Role of Lattice Vibrations in Adatom Diffusion at Metal Stepped Surfaces

International Nuclear Information System (INIS)

Durakanoglu, S.

2004-01-01

Diffusion of a single atom on metal surfaces remains a subject of continuing interest in the surface science community because of the important role it plays in several technologically important phenomena such as thin-film and eptaxial growth, catalysis and chemical reactions. Except for a few studies, most of theoretical works, ranging from molecular dynamic simulations to first principle electronic structure calculations, are devoted to determination of the characteristics of the diffusion processes and the energy barriers, neglecting the contribution of lattice vibrations in adatom diffusion. However, in a series of theoretical works on self-diffusion on the flat surfaces of Cu(100), Ag(100) and Ni(100), Ulrike et al.[1-3], showed that the vibrational contributions are important and should be included in any complete description of the temperature dependence of the diffusion coefficient. In this work, it is our aim to examine the role of lattice vibrations in adatom diffusion at stepped surfaces of Cu(100) and Ni(100) within the framework of transition state theory. Ehrlich-Shwoebel energy barriers for an adatom diffusing over a step-edge are calculated through the inclusion of vibrational internal energy. Local vibrational density of states, main ingredient to the vibrational thermodynamic functions, are calculated in the harmonic approximation, using real space Green's function method with the force constants derived from interaction potentials based on the embedded atom method. We emphasize the sensitivity of the local vibrational density of states to the local atomic environment. We, furthermore, discuss the contribution of thermodynamic functions calculated from local vibrational density of states to the prefactors in diffusion coefficient

Effects of surface relaxation and reconstruction on the vibration characteristics of nanobeams

International Nuclear Information System (INIS)

Zhang, Wen-Ming; Hu, Kai-Ming; Peng, Zhi-Ke; Meng, Guang; Yang, Bin

2016-01-01

Surface effects on the free vibration characteristics of nanobeams are investigated by a modified continuum model. In this paper, the relationship between the parameters of the modified continuum model of surface effects including surface elasticity, surface density, and residual surface stresses, and the parameters of the atomistic lattice model such as surface relaxation and reconstruction in nanobeams is characterized by an atomistic lattice model. The surface effects are incorporated into nanobeams to develop a modified continuum model depicting the free vibrational behavior of nanobeams. The model is validated with the experimental data of an effective size-dependent Young’s modulus and the previous theoretical results. The results demonstrate that both surface elasticity and surface density vary exponentially with surface layer thickness. Therefore, surface elasticity and density can be affected by surface relaxation and residual surface stresses can be induced by surface reconstruction. The natural frequencies of doubly clamped nanobeams can be affected by the dimensions of the nanobeams, surface layer thickness, and residual surface stress. This work may be helpful for understanding surface effects and their influence on the vibrational behavior of nanobeams. (paper)

Vibrational Micro-Spectroscopy of Human Tissues Analysis: Review.

Science.gov (United States)

Bunaciu, Andrei A; Hoang, Vu Dang; Aboul-Enein, Hassan Y

2017-05-04

Vibrational spectroscopy (Infrared (IR) and Raman) and, in particular, micro-spectroscopy and micro-spectroscopic imaging have been used to characterize developmental changes in tissues, to monitor these changes in cell cultures and to detect disease and drug-induced modifications. The conventional methods for biochemical and histophatological tissue characterization necessitate complex and "time-consuming" sample manipulations and the results are rarely quantifiable. The spectroscopy of molecular vibrations using mid-IR or Raman techniques has been applied to samples of human tissue. This article reviews the application of these vibrational spectroscopic techniques for analysis of biological tissue published between 2005 and 2015.

Vibrational spectroscopic study and NBO analysis on tranexamic acid using DFT method

Science.gov (United States)

Muthu, S.; Prabhakaran, A.

2014-08-01

In this work, we reported the vibrational spectra of tranexamic acid (TA) by experimental and quantum chemical calculation. The solid phase FT-Raman and FT-IR spectra of the title compound were recorded in the region 4000 cm-1 to 100 cm-1 and 4000 cm-1 to 400 cm-1 respectively. The molecular geometry, harmonic vibrational frequencies and bonding features of TA in the ground state have been calculated by using density functional theory (DFT) B3LYP method with standard 6-31G(d,p) basis set. The scaled theoretical wavenumber showed very good agreement with the experimental values. The vibrational assignments were performed on the basis of the potential energy distribution (PED) of the vibrational modes. Stability of the molecule, arising from hyperconjugative interactions and charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The results show that ED in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. The electrostatic potential mapped onto an isodensity surface has been obtained. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The thermodynamic properties (heat capacity, entropy, and enthalpy) of the title compound at different temperatures were calculated in gas phase.

Theoretical studies on CH+ ion molecule using configuration interaction method and its spectroscopic properties

International Nuclear Information System (INIS)

Machado, F.B.C.

1985-01-01

The use of the configuration (CI) method for the calculation of very accurate potential energy curves and dipole moment functions, and then their use in the comprehension of spectroscopic properties of diatomic molecules is presented. The spectroscopic properties of CH + and CD + such as: vibrational levels, spectroscopic constants, averaged dipole moments for all vibrational levels, radiative transition probabilities for emission and absorption, and radiative lifetimes are verificated. (M.J.C.) [pt

The impact of accelerometer mounting methods on the level of vibrations recorded at ground surface

Directory of Open Access Journals (Sweden)

Krzysztof Czech

2014-08-01

Full Text Available The paper presents the results of field research based on the measurements of accelerations recorded at ground surface. The source of the vibration characterized by high repetition rate of pulse parameters was light falling weight deflectometer ZFG-01. Measurements of vibrations have been carried out using top quality high-precision measuring system produced by Brüel&Kiær. Accelerometers were mounted on a sandy soil surface at the measuring points located radially at 5-m and 10-m distances from the source of vibration. The paper analyses the impact that the method of mounting accelerometers on the ground has on the level of the recorded values of accelerations of vibrations. It has been shown that the method of attaching the sensor to the surface of the ground is crucial for the credibility of the performed measurements.[b]Keywords[/b]: geotechnics, surface vibrations, ground, vibration measurement

Spectroscopic link between adsorption site occupation and local surface chemical reactivity

DEFF Research Database (Denmark)

Baraldi, A.; Lizzit, S.; Comelli, G.

2004-01-01

rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface...

Coherent vibrational dynamics

CERN Document Server

Lanzani, Guglielmo; De Silvestri, Sandro

2007-01-01

Vibrational spectroscopy is a powerful investigation tool for a wide class of materials covering diverse areas in physics, chemistry and biology. The continuous development in the laser field regarding ultrashort pulse generation has led to the possibility of producing light pulses that can follow vibrational motion coupled to the electronic transitions in molecules and solids in real time. Aimed at researchers and graduate students using vibrational spectroscopy, this book provides both introductory chapters as well as more advanced contents reporting on recent progress. It also provides a good starting point for scientists seeking a sound introduction to ultrafast optics and spectroscopic techniques.

Autonomous target recognition using remotely sensed surface vibration measurements

Science.gov (United States)

Geurts, James; Ruck, Dennis W.; Rogers, Steven K.; Oxley, Mark E.; Barr, Dallas N.

1993-09-01

The remotely measured surface vibration signatures of tactical military ground vehicles are investigated for use in target classification and identification friend or foe (IFF) systems. The use of remote surface vibration sensing by a laser radar reduces the effects of partial occlusion, concealment, and camouflage experienced by automatic target recognition systems using traditional imagery in a tactical battlefield environment. Linear Predictive Coding (LPC) efficiently represents the vibration signatures and nearest neighbor classifiers exploit the LPC feature set using a variety of distortion metrics. Nearest neighbor classifiers achieve an 88 percent classification rate in an eight class problem, representing a classification performance increase of thirty percent from previous efforts. A novel confidence figure of merit is implemented to attain a 100 percent classification rate with less than 60 percent rejection. The high classification rates are achieved on a target set which would pose significant problems to traditional image-based recognition systems. The targets are presented to the sensor in a variety of aspects and engine speeds at a range of 1 kilometer. The classification rates achieved demonstrate the benefits of using remote vibration measurement in a ground IFF system. The signature modeling and classification system can also be used to identify rotary and fixed-wing targets.

Statistical analysis of surface roughness in turning based on cutting parameters and tool vibrations with response surface methodology (RSM)

Science.gov (United States)

Touati, Soufiane; Mekhilef, Slimane

2018-03-01

In this paper, we present an experimental study to determine the effect of the cutting conditions and tool vibration on the surface roughness in finish turning of 32CrMoV12-28 steel, using carbide cutting tool YT15. For these purposes, a linear quadratic model in interaction of connecting surface roughness (Ra, Rz) with different combinations of cutting parameters such as cutting speed, feed rate, depth of cut and tool vibration, in radial and in tangential cutting force directions (Vy) and (Vz) is elaborated. In order to express the degree of interaction of cutting parameters and tool vibration, a multiple linear regression and response surface methodology are adopted. The application of this statistical technique for predicting the surface roughness shows that the feed rate is the most dominant factor followed by the cutting speed. However, the depth of the cut and tool vibrations have secondary effect. The presented models have some interest since they are used in the cutting process optimization.

Nonlinear spectroscopic studies of chiral media

International Nuclear Information System (INIS)

Belkin, Mikhail Alexandrovich

2004-01-01

Molecular chirality plays an important role in chemistry, biology, and medicine. Traditional optical techniques for probing chirality, such as circular dichroism and Raman optical activity rely on electric-dipole forbidden transitions. As a result, their intrinsic low sensitivity limits their use to probe bulk chirality rather than chiral surfaces, monolayers or thin films often important for chemical or biological systems. Contrary to the traditional chirality probes, chiral signal in sum-frequency generation (SFG) is electric-dipole allowed both on chiral surface and in chiral bulk making it a much more promising tool for probing molecular chirality. SFG from a chiral medium was first proposed in 1965, but had never been experimentally confirmed until this thesis work was performed. This thesis describes a set of experiments successfully demonstrating that chiral SFG responses from chiral monolayers and liquids are observable. It shows that, with tunable inputs, SFG can be used as a sensitive spectroscopic tool to probe chirality in both electronic and vibrational resonances of chiral molecules. The monolayer sensitivity is feasible in both cases. It also discusses the relevant theoretical models explaining the origin and the strength of the chiral signal in vibrational and electronic SFG spectroscopies

Sum-frequency spectroscopic studies: I. Surface melting of ice, II. Surface alignment of polymers

Energy Technology Data Exchange (ETDEWEB)

Wei, Xing [Univ. of California, Berkeley, CA (United States)

2000-01-01

Surface vibrational spectroscopy via infrared-visible sum-frequency generation (SFG) has been established as a useful tool to study the structures of different kinds of surfaces and interfaces. This technique was used to study the (0001) face of hexagonal ice (Ih). SFG spectra in the O-H stretch frequency range were obtained at various sample temperatures. For the vapor(air)/ice interface, the degree of orientational order of the dangling OH bonds at the surface was measured as a function of temperature. Disordering sets in around 200 K and increases dramatically with temperature, which is strong evidence of surface melting of ice. For the other ice interfaces (silica/OTS/ice and silica/ice), a similar temperature dependence of the hydrogen bonded OH stretch peak was observed; the free OH stretch mode, however, appears to be different from that of the vapor (air)/ice interface due to interactions at the interfaces. The technique was also used to measure the orientational distributions of the polymer chains on a rubbed polyvinyl alcohol surface. Results show that the polymer chains at the surface appear to be well aligned by rubbing, and the adsorbed liquid crystal molecules are aligned, in turn, by the surface polymer chains. A strong correlation exists between the orientational distributions of the polymer chains and the liquid crystal molecules, indicating that the surface-induced bulk alignment of a liquid crystal film by rubbed polymer surfaces is via an orientational epitaxy-like mechanism. This thesis also contains studies on some related issues that are crucial to the above applications. An experiment was designed to measure SFG spectra in both reflection and transmission. The result confirms that SFG in reflection is generally dominated by the surface contribution. Another issue is the motional effect due to fast orientational motion of molecules at a surface or interface. Calculations show that the effect is significant if the molecular orientation varies

Sum frequency generation vibrational spectroscopy (SFG-VS) for complex molecular surfaces and interfaces: Spectral lineshape measurement and analysis plus some controversial issues

Science.gov (United States)

Wang, Hong-Fei

2016-12-01

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Dynamic Wetting Behavior of Vibrated Droplets on a Micropillared Surface

Directory of Open Access Journals (Sweden)

Zhi-hai Jia

2016-01-01

Full Text Available The dynamical wetting behavior has been observed under vertical vibration of a water droplet placed on a micropillared surface. The wetting transition takes place under the different processes. In compression process, the droplet is transited from Cassie state to Wenzel state. The droplet undergoes a Wenzel-Cassie wetting transition in restoring process and the droplet bounces off from the surface in bouncing process. Meanwhile, the wetting and dewetting models during vibration are proposed. The wetting transition is confirmed by the model calculation. This study has potential to be used to control the wetting state.

Surface Acoustic Wave Vibration Sensors for Measuring Aircraft Flutter

Science.gov (United States)

Wilson, William C.; Moore, Jason P.; Juarez, Peter D.

2016-01-01

Under NASA's Advanced Air Vehicles Program the Advanced Air Transport Technology (AATT) Project is investigating flutter effects on aeroelastic wings. To support that work a new method for measuring vibrations due to flutter has been developed. The method employs low power Surface Acoustic Wave (SAW) sensors. To demonstrate the ability of the SAW sensor to detect flutter vibrations the sensors were attached to a Carbon fiber-reinforced polymer (CFRP) composite panel which was vibrated at six frequencies from 1Hz to 50Hz. The SAW data was compared to accelerometer data and was found to resemble sine waves and match each other closely. The SAW module design and results from the tests are presented here.

Fundamental spectroscopic studies of carbenes and hydrocarbon radicals

Energy Technology Data Exchange (ETDEWEB)

Gottlieb, C.A.; Thaddeus, P. [Harvard Univ., Cambridge, MA (United States)

1993-12-01

Highly reactive carbenes and carbon-chain radicals are studied at millimeter wavelengths by observing their rotational spectra. The purpose is to provide definitive spectroscopic identification, accurate spectroscopic constants in the lowest vibrational states, and reliable structures of the key intermediates in reactions leading to aromatic hydrocarbons and soot particles in combustion.

Surface quality prediction model of nano-composite ceramics in ultrasonic vibration-assisted ELID mirror grinding

Energy Technology Data Exchange (ETDEWEB)

Zhao, Bo; Chen, Fan; Jia, Xiao-feng; Zhao, Chong-yang; Wang, Xiao-bo [Henan Polytechnic University, Jiaozuo (China)

2017-04-15

Ultrasonic vibration-assisted Electrolytic in-process dressing (ELID) grinding is a highly efficient and highly precise machining method. The surface quality prediction model in ultrasonic vibration-assisted ELID mirror grinding was studied. First, the interaction between grits and workpiece surface was analyzed according to kinematic mechanics, and the surface roughness model was developed. The variations in surface roughness under different parameters was subsequently calculated and analyzed by MATLAB. Results indicate that compared with the ordinary ELID grinding, ultrasonic vibration-assisted ELID grinding is superior, because it has more stable and better surface quality and has an improved range of ductile machining.

Spectroscopic studies on surface reactions between minerals and reagents in flotation systems

International Nuclear Information System (INIS)

Giesekke, E.W.

1981-01-01

A study of the adsorbed species at the interface between the minerals and the aqueous solution is reported in the hope that it will contribute to a better understanding of selective mineral flotation by various reagents. The results of infrared spectroscopic studies are cited from the author's investigation on the fluorite-sodium oleate and fluorite-linoleate systems. Electron-spectroscopic techniques, e.g., electron spectroscopy for chemical analysis (ESCA) have also been useful in the identification of adsorbed species on mineral surfaces. Some experimental data from the literature are discussed. These studies have the disadvantage that they are not in situ investigations of the interface between the mineral and the aqueous solution. The potential use of other spectroscopic techniques are discussed, photo-acoustic, Raman, and electron-spin-resonance spectroscopy being considered as possible alternatives. It is suggested that the relatively small surface areas of minerals used in flotation (i.e. smaller than 2m 2 .g- 1 ) impose severe restrictions on the use of such techniques

Theoretical studies for the N2–N2O van der Waals complex: The potential energy surface, intermolecular vibrations, and rotational transition frequencies

International Nuclear Information System (INIS)

Zheng, Rui; Zheng, Limin; Yang, Minghui; Lu, Yunpeng

2015-01-01

Theoretical studies of the potential energy surface (PES) and bound states are performed for the N 2 –N 2 O van der Waals (vdW) complex. A four-dimensional intermolecular PES is constructed at the level of single and double excitation coupled-cluster method with a non-iterative perturbation treatment of triple excitations [CCSD(T)] with aug-cc-pVTZ basis set supplemented with bond functions. Two equivalent T-shaped global minima are located, in which the O atom of N 2 O monomer is near the N 2 monomer. The intermolecular fundamental vibrational states are assigned by inspecting the orientation of the nodal surface of the wavefunctions. The calculated frequency for intermolecular disrotation mode is 23.086 cm −1 , which is in good agreement with the available experimental data of 22.334 cm −1 . A negligible tunneling splitting with the value of 4.2 MHz is determined for the ground vibrational state and the tunneling splitting increases as the increment of the vibrational frequencies. Rotational levels and transition frequencies are calculated for both isotopomers 14 N 2 –N 2 O and 15 N 2 –N 2 O. The accuracy of the PES is validated by the good agreement between theoretical and experimental results for the transition frequencies and spectroscopic parameters

CONDITIONS FOR STABLE CHIP BREAKING AND PROVISION OF MACHINED SURFACE QUALITY WHILE TURNING WITH ASYMMETRIC TOOL VIBRATIONS

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V. K. Sheleh

2015-01-01

Full Text Available The paper considers a process of turning structural steel with asymmetric tool vibrations directed along feeding. Asymmetric vibrations characterized by asymmetry coefficient of vibration cycle, their frequency and amplitude are additionally transferred to the tool in the turning process with the purpose to crush chips. Conditions of stable chip breaking and obtaining optimum dimensions of chip elements have been determined in the paper. In order to reduce a negative impact of the vibration amplitude on a cutting process and quality of the machined surfaces machining must be carried out with its minimum value. In this case certain ratio of the tool vibration frequency to the work-piece rotation speed has been ensured in the paper. A formula has been obtained for calculation of this ratio with due account of the expected length of chip elements and coefficient of vibration cycle asymmetry.Influence of the asymmetric coefficient of the tool vibration cycle on roughness of the machined surfaces and cutting tool wear has been determined in the paper. According to the results pertaining to machining of work-pieces made of 45 and ШХ15 steel the paper presents mathematical relationships of machined surface roughness with cutting modes and asymmetry coefficient of tool vibration cycle. Tool feeding being one of the cutting modes exerts the most significant impact on the roughness value and increase of the tool feeding entails increase in roughness. Reduction in coefficient of vibration cycle asymmetry contributes to surface roughness reduction. However, the cutting tool wear occurs more intensive. Coefficient of the vibration cycle asymmetry must be increased in order to reduce wear rate. Therefore, the choice of the coefficient of the vibration cycle asymmetry is based on the parameters of surface roughness which must be obtained after machining and intensity of tool wear rate.The paper considers a process of turning structural steel with asymmetric

Characterizing interstate vibrational coherent dynamics of surface adsorbed catalysts by fourth-order 3D SFG spectroscopy

Science.gov (United States)

Li, Yingmin; Wang, Jiaxi; Clark, Melissa L.; Kubiak, Clifford P.; Xiong, Wei

2016-04-01

We report the first fourth-order 3D SFG spectroscopy of a monolayer of the catalyst Re(diCN-bpy)(CO)3Cl on a gold surface. Besides measuring the vibrational coherences of single vibrational modes, the fourth-order 3D SFG spectrum also measures the dynamics of interstate coherences and vibrational coherences states between two vibrational modes. By comparing the 3D SFG to the corresponding 2D and third-order 3D IR spectroscopy of the same molecules in solution, we found that the interstate coherences exist in both liquid and surface systems, suggesting that the interstate coherence is not disrupted by surface interactions. However, by analyzing the 3D spectral lineshape, we found that the interstate coherences also experience non-negligible homogenous dephasing dynamics that originate from surface interactions. This unique ability of determining interstate vibrational coherence dynamics of the molecular monolayer can help in understanding of how energy flows within surface catalysts and other molecular monolayers.

The Investigations of Friction under Die Surface Vibration in Cold Forging Process

DEFF Research Database (Denmark)

Jinming, Sha

investigation, and the second stage is to design and manufacture a more practical tool system which can be used to forging some industrial components with larger capacity. The high performance and power piezoelectric actuator stack as the vibration source will be used for designing the vibration system in order...... to 50% with vibration being applied in forming process. Furthermore, by using finite element method, a series of the simulations of the cold forging process under die surface excitation have been implemented in order to further understand the influence of vibration on friction, especially the influence...

Substrate Vibrations as Promoters of Chemical Reactivity on Metal Surfaces.

Science.gov (United States)

Campbell, Victoria L; Chen, Nan; Guo, Han; Jackson, Bret; Utz, Arthur L

2015-12-17

Studies exploring how vibrational energy (Evib) promotes chemical reactivity most often focus on molecular reagents, leaving the role of substrate atom motion in heterogeneous interfacial chemistry underexplored. This combined theoretical and experimental study of methane dissociation on Ni(111) shows that lattice atom motion modulates the reaction barrier height during each surface atom's vibrational period, which leads to a strong variation in the reaction probability (S0) with surface temperature (Tsurf). State-resolved beam-surface scattering studies at Tsurf = 90 K show a sharp threshold in S0 at translational energy (Etrans) = 42 kJ/mol. When Etrans decreases from 42 kJ/mol to 34 kJ/mol, S0 decreases 1000-fold at Tsurf = 90 K, but only 2-fold at Tsurf = 475 K. Results highlight the mechanism for this effect, provide benchmarks for DFT calculations, and suggest the potential importance of surface atom induced barrier height modulation in heterogeneously catalyzed reactions, particularly on structurally labile nanoscale particles and defect sites.

Investigation of silicate mineral sanidine by vibrational and NMR spectroscopic methods

Science.gov (United States)

Anbalagan, G.; Sankari, G.; Ponnusamy, S.; kumar, R. Thilak; Gunasekaran, S.

2009-10-01

Sanidine, a variety of feldspar minerals has been investigated through optical absorption, vibrational (IR and Raman), EPR and NMR spectroscopic techniques. The principal reflections occurring at the d-spacings, 3.2892, 3.2431, 2.9022 and 2.6041 Å confirm the presence of sanidine structure in the mineral. Sanidine shows five prominent characteristic infrared absorption bands in the region 1200-950, 770-720, 590-540 and 650-640 cm -1. The Raman spectrum shows the strongest band at 512 cm -1 characteristic of the feldspar structure, which contains four membered rings of tetrahedra. The UV-vis-NIR absorption spectrum had strong absorption features at 6757, 5780 and 5181 cm -1 due to the combination of fundamental OH- stretching. The bands at 11236 and 8196 cm -1and the strong, well-defined band at (30303 cm -1 attest the presence of Fe 2+ and Fe 3+, respectively, in the sample. The signals at g = 4.3 and 3.7 are interpreted in terms of Fe 3+ at two distinct tetrahedral positions Tl and T2 of the monoclinic crystal structure The 29Si NMR spectrum shows two peaks at -97 and -101 ppm corresponding to T2 and T1, respectively, and one peak in 27Al NMR for Al(IV).

Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

International Nuclear Information System (INIS)

Thompson, Michael C.; Weber, J. Mathias; Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

2015-01-01

We report infrared spectra of nitromethane anion, CH 3 NO 2 − , in the region 700–2150 cm −1 , obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states

Vertical components of surface vibrations induced by mining tremors in the Upper Silesian Coalfield, Poland

International Nuclear Information System (INIS)

Maciag, E.; Kowalski, W.

1997-01-01

Characteristics of vertical components of surface vibration is epicentral zones due to mining tremors in the Upper Silesian Coalfield (USC) are analysed. Both maximum acceleration amplitudes and dominant frequencies of vertical (Z) and horizontal (N-S and E-W) components of vibrations are compared. The role played by the vertical components of vibrations in estimates of hazard for surface structures excited by mining tremors is discussed. 8 refs., 7 figs

Optimization of Surface Finish in Turning Operation by Considering the Machine Tool Vibration using Taguchi Method

Directory of Open Access Journals (Sweden)

Muhammad Munawar

2012-01-01

Full Text Available Optimization of surface roughness has been one of the primary objectives in most of the machining operations. Poor control on the desired surface roughness generates non conforming parts and results into increase in cost and loss of productivity due to rework or scrap. Surface roughness value is a result of several process variables among which machine tool condition is one of the significant variables. In this study, experimentation was carried out to investigate the effect of machine tool condition on surface roughness. Variable used to represent machine tool\\'s condition was vibration amplitude. Input parameters used, besides vibration amplitude, were feed rate and insert nose radius. Cutting speed and depth of cut were kept constant. Based on Taguchi orthogonal array, a series of experimentation was designed and performed on AISI 1040 carbon steel bar at default and induced machine tool\\'s vibration amplitudes. ANOVA (Analysis of Variance, revealed that vibration amplitude and feed rate had moderate effect on the surface roughness and insert nose radius had the highest significant effect on the surface roughness. It was also found that a machine tool with low vibration amplitude produced better surface roughness. Insert with larger nose radius produced better surface roughness at low feed rate.

Model Catalysis of Ammonia Synthesis ad Iron-Water Interfaces - ASum Frequency Generation Vibrational Spectroscopic Study of Solid-GasInterfaces and Anion Photoelectron Spectroscopic Study of Selected Anionclusters

Energy Technology Data Exchange (ETDEWEB)

Ferguson, Michael James [Univ. of California, Berkeley, CA (United States)

2005-01-01

The ammonia synthesis reaction has been studied using single crystal model catalysis combined with sum frequency generation (SFG) vibrational spectroscopy. The adsorption of gases N₂, H₂, O₂ and NH₃ that play a role in ammonia synthesis have been studied on the Fe(111) crystal surface by sum frequency generation vibrational spectroscopy using an integrated Ultra-High Vacuum (UHV)/high-pressure system. SFG spectra are presented for the dissociation intermediates, NH₂ (~3325 cm^-1) and NH (~3235 cm^-1) under high pressure of ammonia or equilibrium concentrations of reactants and products on Fe(111) surfaces. Special attention was paid to understand how potassium promotion of the iron catalyst affects the intermediates of ammonia synthesis. An Fe(111) surface promoted with 0.2 monolayers of potassium red shifts the vibrational frequencies of the reactive surface intermediates, NH and NH₂, providing evidence for weakened the nitrogen-hydrogen bonds relative to clean Fe(111). Spectral features of these surface intermediates persisted to higher temperatures for promoted iron surfaces than for clean Fe(111) surfaces implying that nitrogen-iron bonds are stronger for the promoted surface. The ratio of the NH to NH₂ signal changed for promoted surfaces in the presence of equilibrium concentrations of reactants and products. The order of adding oxygen and potassium to promoted surfaces does not alter the spectra indicating that ammonia induces surface reconstruction of the catalyst to produce the same surface morphology. When oxygen is co-adsorbed with nitrogen, hydrogen, ammonia or potassium on Fe(111), a relative phase shift of the spectra occurs as compared to the presence of adsorbates on clean iron surfaces. Water adsorption on iron was also probed using SFG vibrational spectroscopy. For both H₂O and D₂O, the only spectral feature was in the range of

Quantification of acute vocal fold epithelial surface damage with increasing time and magnitude doses of vibration exposure.

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Tsuyoshi Kojima

Full Text Available Because the vocal folds undergo repeated trauma during continuous cycles of vibration, the epithelium is routinely susceptible to damage during phonation. Excessive and prolonged vibration exposure is considered a significant predisposing factor in the development of vocal fold pathology. The purpose of the present study was to quantify the extent of epithelial surface damage following increased time and magnitude doses of vibration exposure using an in vivo rabbit phonation model. Forty-five New Zealand white breeder rabbits were randomized to nine groups and received varying phonation time-doses (30, 60, or 120 minutes and magnitude-doses (control, modal intensity phonation, or raised intensity phonation of vibration exposure. Scanning electron microscopy and transmission electron microscopy was used to quantify the degree of epithelial surface damage. Results revealed a significant reduction in microprojection density, microprojection height, and depth of the epithelial surface with increasing time and phonation magnitudes doses, signifying increased epithelial surface damage risk with excessive and prolonged vibration exposure. Destruction to the epithelial cell surface may provide significant insight into the disruption of cell function following prolonged vibration exposure. One important goal achieved in the present study was the quantification of epithelial surface damage using objective imaging criteria. These data provide an important foundation for future studies of long-term tissue recovery from excessive and prolonged vibration exposure.

Neutron vibrational spectroscopic studies of novel tire-derived carbon materials.

Science.gov (United States)

Li, Yunchao; Cheng, Yongqiang; Daemen, Luke L; Veith, Gabriel M; Levine, Alan M; Lee, Richard J; Mahurin, Shannon M; Dai, Sheng; Naskar, Amit K; Paranthaman, Mariappan Parans

2017-08-23

Sulfonated tire-derived carbons have been demonstrated to be high value-added carbon products of tire recycling in several energy storage system applications including lithium, sodium, potassium ion batteries and supercapacitors. In this communication, we compared different temperature pyrolyzed sulfonated tire-derived carbons with commercial graphite and unmodified/non-functionalized tire-derived carbon by studying the surface chemistry and properties, vibrational spectroscopy of the molecular structure, chemical bonding such as C-H bonding, and intermolecular interactions of the carbon materials. The nitrogen adsorption-desorption studies revealed the tailored micro and meso pore size distribution of the carbon during the sulfonation process. XPS and neutron vibrational spectra showed that the sulfonation of the initial raw tire powders could remove the aliphatic hydrogen containing groups ([double bond splayed left]CH 2 and -CH 3 groups) and reduce the number of heteroatoms that connect to carbon. The absence of these functional groups could effectively improve the first cycle efficiency of the material in rechargeable batteries. Meanwhile, the introduced -SO 3 H functional group helped in producing terminal H at the edge of the sp 2 bonded graphite-like layers. This study reveals the influence of the sulfonation process on the recovered hard carbon from used tires and provides a pathway to develop and improve advanced energy storage materials.

Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

Science.gov (United States)

Uma Maheswari, J; Muthu, S; Sundius, Tom

2014-04-05

A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths λmax were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. Copyright © 2014 Elsevier B.V. All rights reserved.

Theoretical and vibrational spectroscopic approach to keto-enol tautomerism in methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate

Science.gov (United States)

Arı, Hatice; Özpozan, Talat; Büyükmumcu, Zeki; Kabacalı, Yiğit; Saçmaci, Mustafa

2016-10-01

A carbamate compound having tricarbonyl groups, methyl-2-(4-methoxybenzoyl)-3-(4-methoxyphenyl)-3-oxopropanoylcarbamate (BPOC) was investigated from theoretical and vibrational spectroscopic point of view employing quantum chemical methods. Hybrid Density Functionals (B3LYP, X3LYP and B3PW91) with 6-311 G(d,p) basis set were used for the calculations. Rotational barrier and conformational analyses were performed to find the most stable conformers of keto and enol forms of the molecule. Three transition states for keto-enol tautomerism in gas phase were determined. The results of the calculations show that enol-1 form of BPOC is more stable than keto and enol-2 forms. Hydrogen bonding investigation including Natural bond orbital analysis (NBO) for all the tautomeric structures was employed to compare intra-molecular interactions. The energies of HOMO and LUMO molecular orbitals for all tautomeric forms of BPOC were predicted. Normal Coordinate Analysis (NCA) was carried out for the enol-1 to assign vibrational bands of IR and Raman spectra. The scaling factors were calculated as 0.9721, 0.9697 and 0.9685 for B3LYP, X3LYP and B3PW91 methods, respectively. The correlation graphs of experimental versus calculated vibrational wavenumbers were plotted and X3LYP method gave better frequency agreement than the others.

Vibration attenuation and shape control of surface mounted, embedded smart beam

Directory of Open Access Journals (Sweden)

Vivek Rathi

Full Text Available Active Vibration Control (AVC using smart structure is used to reduce the vibration of a system by automatic modification of the system structural response. AVC is widely used, because of its wide and broad frequency response range, low additional mass, high adaptability and good efficiency. A lot of research has been done on Finite Element (FE models for AVC based on Euler Bernoulli Beam Theory (EBT. In the present work Timoshenko Beam Theory (TBT is used to model a smart cantilever beam with surface mounted sensors / actuators. A Periodic Output Feedback (POF Controller has been designed and applied to control the first three modes of vibration of a flexible smart cantilever beam. The difficulties encountered in the usage of surface mounted piezoelectric patches in practical situations can be overcome by the use of embedded shear sensors / actuators. A mathematical model of a smart cantilever beam with embedded shear sensors and actuators is developed. A POF Controller has been designed and applied to control of vibration of a flexible smart cantilever beam and effect of actuator location on the performance of the controller is investigated. The mathematical modeling and control of a Multiple Input multiple Output (MIMO systems with two sensors and two actuators have also been considered.

Capturing inhomogeneous broadening of the -CN stretch vibration in a Langmuir monolayer with high-resolution spectra and ultrafast vibrational dynamics in sum-frequency generation vibrational spectroscopy (SFG-VS)

Science.gov (United States)

Velarde, Luis; Wang, Hong-fei

2013-08-01

While in principle the frequency-domain and time-domain spectroscopic measurements should generate identical information for a given molecular system, the inhomogeneous character of surface vibrations in sum-frequency generation vibrational spectroscopy (SFG-VS) studies has only been studied with time-domain SFG-VS by mapping the decay of the vibrational polarization using ultrafast lasers, this due to the lack of SFG vibrational spectra with high enough spectral resolution and accurate enough lineshape. Here, with the recently developed high-resolution broadband SFG-VS (HR-BB-SFG-VS) technique, we show that the inhomogeneous lineshape can be obtained in the frequency-domain for the anchoring CN stretch of the 4-n-octyl-4'-cyanobiphenyl (8CB) Langmuir monolayer at the air-water interface, and that an excellent agreement with the time-domain SFG free-induction-decay can be established. We found that the 8CB CN stretch spectrum consists of a single peak centered at 2234.00 ± 0.01 cm-1 with a total linewidth of 10.9 ± 0.3 cm-1 at half maximum. The Lorentzian contribution accounts only for 4.7 ± 0.4 cm-1 to this width and the Gaussian (inhomogeneous) broadening for as much as 8.1 ± 0.2 cm-1. Polarization analysis of the -CN spectra showed that the -CN group is tilted 57° ± 2° from the surface normal. The large heterogeneity in the -CN spectrum is tentatively attributed to the -CN group interactions with the interfacial water molecules penetrated/accommodated into the 8CB monolayer, a unique phenomenon for the nCB Langmuir monolayers reported previously.

Calculations on the vibrational level density in highly excited formaldehyde

International Nuclear Information System (INIS)

Rashev, Svetoslav; Moule, David C.

2003-01-01

The object of the present work is to develop a model that provides realistic estimates of the vibrational level density in polyatomic molecules in a given electronic state, at very high (chemically relevant) vibrational excitation energies. For S 0 formaldehyde (D 2 CO), acetylene, and a number of triatomics, the estimates using conventional spectroscopic formulas have yielded densities at the dissociation threshold, very much lower than the experimentally measured values. In the present work we have derived a general formula for the vibrational energy levels of a polyatomic molecule, which is a generalization of the conventional Dunham spectroscopic expansion. Calculations were performed on the vibrational level density in S 0 D 2 CO, H 2 C 2 , and NO 2 at excitation energies in the vicinity of the dissociation limit, using the newly derived formula. The results from the calculations are in reasonable agreement with the experimentally measured data

Investigation of sandwich material surface created by abrasive water jet (AWJ via vibration emission

Directory of Open Access Journals (Sweden)

P. Hreha

2014-01-01

Full Text Available The paper presents research a of abrasive waterjet cutting of heterogeneous “sandwich“ material with different Young modulus of elasticity of the cutted surface geometry by means of vibration emission. In order to confirm hypothetical assumptions about direct relation between vibration emission and surface quality an experiment in heterogeneous material consisting of stainless steel (DIN 1.4006 / AISI 410 and alloy AlCuMg2 has been provided.

Vibrational Surface Electron-Energy-Loss Spectroscopy Probes Confined Surface-Phonon Modes

Directory of Open Access Journals (Sweden)

Hugo Lourenço-Martins

2017-12-01

Full Text Available Recently, two reports [Krivanek et al. Nature (London 514, 209 (2014NATUAS0028-083610.1038/nature13870, Lagos et al. Nature (London 543, 529 (2017NATUAS0028-083610.1038/nature21699] have demonstrated the amazing possibility to probe vibrational excitations from nanoparticles with a spatial resolution much smaller than the corresponding free-space phonon wavelength using electron-energy-loss spectroscopy (EELS. While Lagos et al. evidenced a strong spatial and spectral modulation of the EELS signal over a nanoparticle, Krivanek et al. did not. Here, we show that discrepancies among different EELS experiments as well as their relation to optical near- and far-field optical experiments [Dai et al. Science 343, 1125 (2014SCIEAS0036-807510.1126/science.1246833] can be understood by introducing the concept of confined bright and dark surface phonon modes, whose density of states is probed by EELS. Such a concise formalism is the vibrational counterpart of the broadly used formalism for localized surface plasmons [Ouyang and Isaacson Philos. Mag. B 60, 481 (1989PMABDJ1364-281210.1080/13642818908205921, García de Abajo and Aizpurua Phys. Rev. B 56, 15873 (1997PRBMDO0163-182910.1103/PhysRevB.56.15873, García de Abajo and Kociak Phys. Rev. Lett. 100, 106804 (2008PRLTAO0031-900710.1103/PhysRevLett.100.106804, Boudarham and Kociak Phys. Rev. B 85, 245447 (2012PRBMDO1098-012110.1103/PhysRevB.85.245447]; it makes it straightforward to predict or interpret phenomena already known for localized surface plasmons such as environment-related energy shifts or the possibility of 3D mapping of the related surface charge densities [Collins et al. ACS Photonics 2, 1628 (2015APCHD52330-402210.1021/acsphotonics.5b00421].

The molecular structure of the borate mineral inderite Mg(H4B3O7)(OH) · 5H2O--a vibrational spectroscopic study.

Science.gov (United States)

Frost, Ray L; López, Andrés; Xi, Yunfei; Lima, Rosa Malena Fernandes; Scholz, Ricardo; Granja, Amanda

2013-12-01

We have undertaken a study of the mineral inderite Mg(H4B3O7)(OH) · 5H2O a hydrated hydroxy borate mineral of magnesium using scanning electron microscopy, thermogravimetry and vibrational spectroscopic techniques. The structure consists of [Formula: see text] soroborate groups and Mg(OH)2(H2O)4 octahedra interconnected into discrete molecules by the sharing of two OH groups. Thermogravimetry shows a mass loss of 47.2% at 137.5 °C, proving the mineral is thermally unstable. Raman bands at 954, 1047 and 1116 cm(-1) are assigned to the trigonal symmetric stretching mode. The two bands at 880 and 916 cm(-1) are attributed to the symmetric stretching mode of the tetrahedral boron. Both the Raman and infrared spectra of inderite show complexity. Raman bands are observed at 3052, 3233, 3330, 3392 attributed to water stretching vibrations and 3459 cm(-1) with sharper bands at 3459, 3530 and 3562 cm(-1) assigned to OH stretching vibrations. Vibrational spectroscopy is used to assess the molecular structure of inderite. Copyright © 2013 Elsevier B.V. All rights reserved.

Chromate adsorption on selected soil minerals: Surface complexation modeling coupled with spectroscopic investigation

Energy Technology Data Exchange (ETDEWEB)

Veselská, Veronika, E-mail: veselskav@fzp.czu.cz [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Fajgar, Radek [Department of Analytical and Material Chemistry, Institute of Chemical Process Fundamentals of the CAS, v.v.i., Rozvojová 135/1, CZ-16502, Prague (Czech Republic); Číhalová, Sylva [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic); Bolanz, Ralph M. [Institute of Geosciences, Friedrich-Schiller-University Jena, Carl-Zeiss-Promenade 10, DE-07745, Jena (Germany); Göttlicher, Jörg; Steininger, Ralph [ANKA Synchrotron Radiation Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, DE-76344, Eggenstein-Leopoldshafen (Germany); Siddique, Jamal A.; Komárek, Michael [Department of Environmental Geosciences, Faculty of Environmental Sciences, Czech University of Life Sciences Prague, Kamýcka 129, CZ-16521, Prague (Czech Republic)

2016-11-15

Highlights: • Study of Cr(VI) adsorption on soil minerals over a large range of conditions. • Combined surface complexation modeling and spectroscopic techniques. • Diffuse-layer and triple-layer models used to obtain fits to experimental data. • Speciation of Cr(VI) and Cr(III) was assessed. - Abstract: This study investigates the mechanisms of Cr(VI) adsorption on natural clay (illite and kaolinite) and synthetic (birnessite and ferrihydrite) minerals, including its speciation changes, and combining quantitative thermodynamically based mechanistic surface complexation models (SCMs) with spectroscopic measurements. Series of adsorption experiments have been performed at different pH values (3–10), ionic strengths (0.001–0.1 M KNO{sub 3}), sorbate concentrations (10{sup −4}, 10{sup −5}, and 10{sup −6} M Cr(VI)), and sorbate/sorbent ratios (50–500). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy were used to determine the surface complexes, including surface reactions. Adsorption of Cr(VI) is strongly ionic strength dependent. For ferrihydrite at pH <7, a simple diffuse-layer model provides a reasonable prediction of adsorption. For birnessite, bidentate inner-sphere complexes of chromate and dichromate resulted in a better diffuse-layer model fit. For kaolinite, outer-sphere complexation prevails mainly at lower Cr(VI) loadings. Dissolution of solid phases needs to be considered for better SCMs fits. The coupled SCM and spectroscopic approach is thus useful for investigating individual minerals responsible for Cr(VI) retention in soils, and improving the handling and remediation processes.

Spectroscopic characterization of the on-surface induced (cyclo) dehydrogenation of a N-heteroaromatic compound on noble metal surfaces

Czech Academy of Sciences Publication Activity Database

Palacio, I.; Pinardi, A. L.; Martínez, J. I.; Preobrajenski, A.; Cossaro, A.; Jančařík, Andrej; Stará, Irena G.; Starý, Ivo; Méndez, J.; Martín-Gago, J.A.; López, M.F.

2017-01-01

Roč. 19, č. 33 (2017), s. 22454-22461 ISSN 1463-9076 Institutional support: RVO:61388963 Keywords : dibenzohelicene * on-surface (cyclo)dehydrogenation * spectroscopic characterization Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 4.123, year: 2016

Ab initio structural and spectroscopic study of HPS{sup x} and HSP{sup x} (x = 0,+1,−1) in the gas phase

Energy Technology Data Exchange (ETDEWEB)

Yaghlane, Saida Ben [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications – LSAMA, Université de Tunis, Tunis (Tunisia); Cotton, C. Eric; Francisco, Joseph S., E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Department of Chemistry and Department of Earth and Atmospheric Science, Purdue University, West Lafayette, Indiana 49707 (United States); Linguerri, Roberto; Hochlaf, Majdi, E-mail: francisc@purdue.edu, E-mail: hochlaf@univ-mlv.fr [Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 5 bd Descartes, 77454 Marne-la-Vallée (France)

2013-11-07

Accurate ab initio computations of structural and spectroscopic parameters for the HPS/HSP molecules and corresponding cations and anions have been performed. For the electronic structure computations, standard and explicitly correlated coupled cluster techniques in conjunction with large basis sets have been adopted. In particular, we present equilibrium geometries, rotational constants, harmonic vibrational frequencies, adiabatic ionization energies, electron affinities, and, for the neutral species, singlet-triplet relative energies. Besides, the full-dimensional potential energy surfaces (PESs) for HPS{sup x} and HSP{sup x} (x = −1,0,1) systems have been generated at the standard coupled cluster level with a basis set of augmented quintuple-zeta quality. By applying perturbation theory to the calculated PESs, an extended set of spectroscopic constants, including τ, first-order centrifugal distortion and anharmonic vibrational constants has been obtained. In addition, the potentials have been used in a variational approach to deduce the whole pattern of vibrational levels up to 4000 cm{sup −1} above the minima of the corresponding PESs.

Surface energy effect on free vibration of nano-sized piezoelectric double-shell structures

Science.gov (United States)

Fang, Xue-Qian; Zhu, Chang-Song; Liu, Jin-Xi; Liu, Xiang-Lin

2018-01-01

Combining Goldenveizer-Novozhilov shell theory, thin plate theory and electro-elastic surface theory, the size-dependent vibration of nano-sized piezoelectric double-shell structures under simply supported boundary condition is presented, and the surface energy effect on the natural frequencies is discussed. The displacement components of the cylindrical nano-shells and annular nano-plates are expanded as the superposition of standard Fourier series based on Hamilton's principle. The total stresses with consideration of surface energy effect are derived, and the total energy function is obtained by using Rayleigh-Ritz energy method. The free vibration equation is solved, and the natural frequency is analyzed. In numerical examples, it is found that the surface elastic constant, piezoelectric constant and surface residual stress show different effects on the natural frequencies. The effect of surface piezoelectric constant is the maximum. The effect of dimensions of the double-shell under different surface material properties is also examined.

Detection of water and its derivatives on individual nanoparticles using vibrational electron energy-loss spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Crozier, Peter A., E-mail: crozier@asu.edu [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States); Aoki, Toshihiro [LeRoy Eyring Center for Solid State Science, Arizona State University, Tempe, AZ 85287-1704 (United States); Liu, Qianlang [School for the Engineering of Matter, Transport and Energy, Arizona State University, 501 E. Tyler Mall, Tempe, AZ 85287-6106 (United States)

2016-10-15

Understanding the role of water, hydrate and hydroxyl species on nanoparticle surfaces and interfaces is very important in both physical and life sciences. Detecting the presence of oxygen-hydrogen species with nanometer resolution is extremely challenging at present. Here we show that the recently developed vibrational electron energy-loss spectroscopy using subnanometer focused electron beams can be employed to spectroscopically identify the local presence and variation of OH species on nanoscale surfaces. The hydrogen-oxygen fingerprint can be correlated with highly localized structural and morphological information obtained from electron imaging. Moreover, the current approach exploits the aloof beam mode of spectral acquisition which does not require direct electron irradiation of the sample thus greatly reducing beam damage to the OH bond. These findings open the door for using electron microscopy to probe local hydroxyl and hydrate species on nanoscale organic and inorganic structures. - Highlights: • High spatial resolution spectroscopic detection of water related species in nanoparticles. • Detection of OH stretch modes with vibrational EELS. • Differentiation between hydrate and hydroxide species on or on nanoparticles. • Detection of hydrate on a single 60 nm oxide nanoparticle of MgO. • Use of aloof beam EELS to minimize radiation damage.

The effect of inclined soil layers on surface vibration from underground railways using a semi-analytical approach

International Nuclear Information System (INIS)

Jones, S; Hunt, H

2009-01-01

Ground vibration due to underground railways is a significant source of disturbance for people living or working near the subways. The numerical models used to predict vibration levels have inherent uncertainty which must be understood to give confidence in the predictions. A semi-analytical approach is developed herein to investigate the effect of soil layering on the surface vibration of a halfspace where both soil properties and layer inclination angles are varied. The study suggests that both material properties and inclination angle of the layers have significant effect (± 10dB) on the surface vibration response.

Vibrational energy on surfaces: Ultrafast flash-thermal conductance of molecular monolayers

Science.gov (United States)

Dlott, Dana

2008-03-01

Vibrational energy flow through molecules remains a perennial problem in chemical physics. Usually vibrational energy dynamics are viewed through the lens of time-dependent level populations. This is natural because lasers naturally pump and probe vibrational transitions, but it is also useful to think of vibrational energy as being conducted from one location in a molecule to another. We have developed a new technique where energy is driven into a specific part of molecules adsorbed on a metal surface, and ultrafast nonlinear coherent vibrational spectroscopy is used to watch the energy arrive at another part. This technique is the analog of a flash thermal conductance apparatus, except it probes energy flow with angstrom spatial and femtosecond temporal resolution. Specific examples to be presented include energy flow along alkane chains, and energy flow into substituted benzenes. Ref: Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Ultrafast flash thermal conductance of molecular chains, Science 317, 787-790 (2007). This material is based upon work supported by the National Science Foundation under award DMR 0504038 and the Air Force Office of Scientific Research under award FA9550-06-1-0235.

Spectroscopic characterization of manganese-doped alkaline earth

Indian Academy of Sciences (India)

The intensity and frequency variations for the characteristic phosphate group vibrations have been correlated with the changes of the structural units present in these glasses. Depolymerization of the phosphate chains in all the glasses is observed with replacement of alkaline earth content by spectroscopic studies.

Spectroscopic and electrooptical manifestations of internal rotation of the outer-sphere cation in Li(PO3) molecule

International Nuclear Information System (INIS)

Romanets, A.V.; Sukhanov, L.P.

1997-01-01

Spectroscopic and electrooptical manifestations of internal molecular rotations in LiPO 3 have been studied on the basis of ab initio calculated surface of potential energy and dipole momentum function using the finite element method. It has been ascertained that tunnel splitting of energy levels with number n, available for vibrational spectroscopy of high resolution, apper in the molecule studied only at n≥13. It is shown that internal rotations in the molecule are able to decrease sharply its polarity on vibration-excited levels, sufficiently far from the vertex of potential barrier of intramolecular regroupings. Difficulties of experimental confirmation of predicted electrooptical effect of structural non-rigidity in the molecule studied are discussed

Isotopic effects in vibrational relaxation dynamics of H on a Si(100) surface

Science.gov (United States)

Bouakline, F.; Lorenz, U.; Melani, G.; Paramonov, G. K.; Saalfrank, P.

2017-10-01

In a recent paper [U. Lorenz and P. Saalfrank, Chem. Phys. 482, 69 (2017)], we proposed a robust scheme to set up a system-bath model Hamiltonian, describing the coupling of adsorbate vibrations (system) to surface phonons (bath), from first principles. The method is based on an embedded cluster approach, using orthogonal coordinates for system and bath modes, and an anharmonic phononic expansion of the system-bath interaction up to second order. In this contribution, we use this model Hamiltonian to calculate vibrational relaxation rates of H-Si and D-Si bending modes, coupled to a fully H(D)-covered Si(100)-( 2 × 1 ) surface, at zero temperature. The D-Si bending mode has an anharmonic frequency lying inside the bath frequency spectrum, whereas the H-Si bending mode frequency is outside the bath Debye band. Therefore, in the present calculations, we only take into account one-phonon system-bath couplings for the D-Si system and both one- and two-phonon interaction terms in the case of H-Si. The computation of vibrational lifetimes is performed with two different approaches, namely, Fermi's golden rule, and a generalized Bixon-Jortner model built in a restricted vibrational space of the adsorbate-surface zeroth-order Hamiltonian. For D-Si, the Bixon-Jortner Hamiltonian can be solved by exact diagonalization, serving as a benchmark, whereas for H-Si, an iterative scheme based on the recursive residue generation method is applied, with excellent convergence properties. We found that the lifetimes obtained with perturbation theory, albeit having almost the same order of magnitude—a few hundred fs for D-Si and a couple of ps for H-Si—, are strongly dependent on the discretized numerical representation of the bath spectral density. On the other hand, the Bixon-Jortner model is free of such numerical deficiencies, therefore providing better estimates of vibrational relaxation rates, at a very low computational cost. The results obtained with this model clearly show

3-D numerical simulation on the vibration of liquid sodium's free surface in sodium pool of FBR

International Nuclear Information System (INIS)

Han Biao; Yao Zhaohui; Ye Hongkai; Wang Xuefang

1997-01-01

This paper succeeds in simulating three-dimensional incompressible flows with free surface, complicated in-flow and out-flow boundary conditions and internal obstacles, and also can treat these fluid flows in arbitrary shape vessel using a partial cell. According to all kinds of the element influencing the free surface's vibration in sodium pool it may give the various wave's form, the highest and lowest position, and the amount of the vibration. This paper introduces the brief principle of VOF numerical method, develops the computational program based on NASA-VOF3D, provides some results about the free surface's vibration in sodium pool of FBR

Finite-Element Simulation of Cantilever Vibrations in Atomic Force Acoustic Microscopy

Energy Technology Data Exchange (ETDEWEB)

Beltran, F J Espinoza [Centro de Investigacion y Estudios Avanzados del IPN. Unidad Queretaro, Apdo. Postal 1-798, 76001 Queretaro, Qro. (Mexico); Scholz, T [Hamburg University of Technology, Institute of Advanced Ceramics, Denickestrasse 15, D-21073 Hamburg (Germany); Schneider, G A [Hamburg University of Technology, Institute of Advanced Ceramics, Denickestrasse 15, D-21073 Hamburg (Germany); Munoz-Saldana, J [Centro de Investigacion y Estudios Avanzados del IPN. Unidad Queretaro, Apdo. Postal 1-798, 76001 Queretaro, Qro. (Mexico); Rabe, U [Fraunhofer Institute for Non-Destructive Testing (IZFP), Bldg. E3.1, University, D-66123 Saarbruecken (Germany); Arnold, W [Fraunhofer Institute for Non-Destructive Testing (IZFP), Bldg. E3.1, University, D-66123 Saarbruecken (Germany)

2007-03-15

Atomic Force Acoustic Microscopy has been proven to be a powerful technique for materials characterization with nanoscale lateral resolution. This technique allows one to obtain images of elastic properties of materials. By means of spectroscopic measurements of the tip-sample contact-resonance frequencies, it is possible to obtain quantitative values of the mechanical stiffness of the sample surface. For quantitative analysis a reliable relation between the spectroscopic data and the contact stiffness is required based on a correct geometrical model of the cantilever vibrations. This model must be precise enough for predicting the resonance frequencies of the tip-sample interaction when excited over a wide range of frequencies. Analytical models have served as a good reference for understanding the vibrational behavior of the AFM cantilever. They have certain limits, however, for reproducing the tip-sample contact-resonances due to the cantilever geometries used. For obtaining the local elastic modulus of samples, it is necessary to know the tip-sample contact area which is usually obtained by a calibration procedure with a reference sample. In this work we show that finiteelement modeling may be used to replace the analytical inversion procedure for AFAM data. First, the three first bending modes of cantilever resonances were used for finding the geometrical dimension of the cantilever employed. Then the normal and in-plane stiffness of the sample were obtained for each measurement on the surface to be measured. A calibration was needed to obtain the tip position of the cantilever by making measurements on a sample with known surface elasticity, here crystalline silicon. The method developed in this work was applied to AFAM measurements on silicon, zerodur, and strontium titanate.

Experimental study of heat transfer enhancement due to the surface vibrations in a flexible double pipe heat exchanger

Science.gov (United States)

Hosseinian, A.; Meghdadi Isfahani, A. H.

2018-04-01

In this study, the heat transfer enhancement due to the surface vibration for a double pipe heat exchanger, made of PVDF, is investigated. In order to create forced vibrations (3-9 m/s2, 100 Hz) on the outer surface of the heat exchanger electro-dynamic vibrators are used. Experiments were performed at inner Reynolds numbers ranging from 2533 to 9960. The effects of volume flow rate and temperature on heat transfer performance are evaluated. Results demonstrated that heat transfer coefficient increases by increasing vibration level and mass flow rate. The most increase in heat transfer coefficient is 97% which is obtained for the highest vibration level (9 m/s2) in the experiment range.

Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

Science.gov (United States)

Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

2014-04-24

In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

Science.gov (United States)

Sørensen, L. K.; Fleig, T.; Olsen, J.

2009-08-01

Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

Spectroscopic and electric properties of the LiCs molecule: a coupled cluster study including higher excitations

International Nuclear Information System (INIS)

Soerensen, L K; Fleig, T; Olsen, J

2009-01-01

Aimed at obtaining complete and highly accurate potential energy surfaces for molecules containing heavy elements, we present a new general-order coupled cluster method which can be applied in the framework of the spin-free Dirac formalism. As an initial application we present a systematic study of electron correlation and relativistic effects on the spectroscopic and electric properties of the LiCs molecule in its electronic ground state. In particular, we closely investigate the importance of excitations higher than coupled cluster doubles, spin-free and spin-dependent relativistic effects and the correlation of outer-core electrons on the equilibrium bond length, the harmonic vibrational frequency, the dissociation energy, the dipole moment and the static electric dipole polarizability. We demonstrate that our new implementation allows for highly accurate calculations not only in the bonding region but also along the complete potential curve. The quality of our results is demonstrated by a vibrational analysis where an almost complete set of vibrational levels has been calculated accurately.

Millimeterwave spectroscopy of active laser plasmas; the excited vibrational states of HCN

International Nuclear Information System (INIS)

De Lucia, F.C.; Helminger, P.A.

1977-01-01

Millimeter and submillimeter microwave techniques have been used for the spectroscopic study of an HCN laser plasma. Forty-seven rotational transitions in 12 excited vibrational states have been observed. Numerous rotational, vibrational, and perturbation parameters have been calculated from these data. A discussion of experimental techniques is included

Vibrational monitor of early demineralization in tooth enamel after in vitro exposure to phosphoridic liquid

Science.gov (United States)

Pezzotti, Giuseppe; Adachi, Tetsuya; Gasparutti, Isabella; Vincini, Giulio; Zhu, Wenliang; Boffelli, Marco; Rondinella, Alfredo; Marin, Elia; Ichioka, Hiroaki; Yamamoto, Toshiro; Marunaka, Yoshinori; Kanamura, Narisato

2017-02-01

The Raman spectroscopic method has been applied to quantitatively assess the in vitro degree of demineralization in healthy human teeth. Based on previous evaluations of Raman selection rules (empowered by an orientation distribution function (ODF) statistical algorithm) and on a newly proposed analysis of phonon density of states (PDOS) for selected vibrational modes of the hexagonal structure of hydroxyapatite, a molecular-scale evaluation of the demineralization process upon in vitro exposure to a highly acidic beverage (i.e., CocaCola™ Classic, pH = 2.5) could be obtained. The Raman method proved quite sensitive and spectroscopic features could be directly related to an increase in off-stoichiometry of the enamel surface structure since the very early stage of the demineralization process (i.e., when yet invisible to other conventional analytical techniques). The proposed Raman spectroscopic algorithm might possess some generality for caries risk assessment, allowing a prompt non-contact diagnostic practice in dentistry.

Foreword: The 12th International Conference on Vibrations at Surfaces (VAS 12) (Erice, 20 26 July 2007)

Science.gov (United States)

Benedek, Giorgio; Vattuone, Luca

2008-06-01

The 12th International Conference on Vibrations at Surfaces (VAS 12) took place from 20 26 July 2007 as an event of the International School of Solid State Physics at the Ettore Majorana Foundation and Centre for Scientific Culture, Erice (Italy). The format and special environment of the conference have contributed to its transition from a traditional, medium-size conference into a more effective workshop, with a series of lectures reporting the most recent developments in the field, two poster sessions presenting recent results and even works in progress being discussed. The papers collected in this issue cover the highlights of the conference very thoroughly. Quite a few novel aspects concerning vibrations at surfaces are represented here, for example: new aspects in surface phonon spectroscopy, such as the very recent progress in inelastic x-ray scattering, the first observation of the boson peak in disordered surfaces, progress in the theory of atom scattering inelastic resonances, the action spectroscopy, the study of polycrystalline surfaces with electron energy-loss spectroscopy etc; parallel developments in experimental vibrational studies of adsorbed phases, either inorganic or organic, with those in ab initio theoretical simulations; the theory of enhanced electron--phonon interaction in low dimensions (2D and 1D); the extension from the traditional realm of surface vibrations and spectroscopy to other aspects of surface dynamics, like friction and various nonlinear effects, and to relevant dynamical phenomena occurring at interfaces. Other novelties presented at the conference, but already published in recent issues of the Journal of Physics: Condensed Matter, are also worth mentioning: the spin-echo spectroscopy with 3He allowing for slow-dynamics spectroscopy at very high, unprecedented resolutions (2007 J. Phys.: Cond. Matter 19 300301 and 305010; the first demonstration of dissociative surface trapping of molecules (2007 J. Phys.: Cond. Matter 19

Behavior of ro-vibrationally excited H2 molecules and H atoms in a plasma expansion

International Nuclear Information System (INIS)

Vankan, P.; Schram, D.C.; Engeln, R.

2005-01-01

The behavior in a supersonic plasma expansion of H atom and H2 molecules, both ground-state and ro-vibrationally excited, is studied using various laser spectroscopic techniques. The ground-state H2 molecules expand like a normal gas. The behavior of H atoms and H 2 rv molecules, on the other hand, is considerably influenced, and to some extend even determined, by their reactivity. The H atoms diffuse out of the expansion due to surface association at the walls of the vacuum vessel. Moreover, by reducing the surface area of the nozzle by a factor of two, the amount of H atoms leaving the source is increased by one order of magnitude, due to a decreased surface association of H atoms in the nozzle. The evolution of the ro-vibrational distributions along the expansion axis shows the relaxation of the molecular hydrogen from the high temperature in the up-stream region to the low ambient temperature in the down-stream region. Whereas the vibrational distribution resembles a Boltzmann distribution, the rotational distribution is a non-equilibrium one, in which the high rotational levels (J > 7) are much more populated than what is expected from the low rotational levels (J <5). We observed overpopulations of up to seven orders of magnitude. The production of the high rotational levels is very probably connected to the surface association in the nozzle

Particle in a Disk: A Spectroscopic and Computational Laboratory Exercise Studying the Polycyclic Aromatic Hydrocarbon Corannulene

Science.gov (United States)

Frey, E. Ramsey; Sygula, Andrzej; Hammer, Nathan I.

2014-01-01

This laboratory exercise introduces undergraduate chemistry majors to the spectroscopic and theoretical study of the polycyclic aromatic hydrocarbon (PAH), corannulene. Students explore the spectroscopic properties of corannulene using UV-vis and Raman vibrational spectroscopies. They compare their experimental results to simulated vibrational…

Optimal placement of trailing-edge flaps for helicopter vibration reduction using response surface methods

Science.gov (United States)

Viswamurthy, S. R.; Ganguli, Ranjan

2007-03-01

This study aims to determine optimal locations of dual trailing-edge flaps to achieve minimum hub vibration levels in a helicopter, while incurring low penalty in terms of required trailing-edge flap control power. An aeroelastic analysis based on finite elements in space and time is used in conjunction with an optimal control algorithm to determine the flap time history for vibration minimization. The reduced hub vibration levels and required flap control power (due to flap motion) are the two objectives considered in this study and the flap locations along the blade are the design variables. It is found that second order polynomial response surfaces based on the central composite design of the theory of design of experiments describe both objectives adequately. Numerical studies for a four-bladed hingeless rotor show that both objectives are more sensitive to outboard flap location compared to the inboard flap location by an order of magnitude. Optimization results show a disjoint Pareto surface between the two objectives. Two interesting design points are obtained. The first design gives 77 percent vibration reduction from baseline conditions (no flap motion) with a 7 percent increase in flap power compared to the initial design. The second design yields 70 percent reduction in hub vibration with a 27 percent reduction in flap power from the initial design.

Detection and Monitoring of Neurotransmitters - a Spectroscopic Analysis

Science.gov (United States)

Manciu, Felicia; Lee, Kendall; Durrer, William; Bennet, Kevin

2012-10-01

In this work we demonstrate the capability of confocal Raman mapping spectroscopy for simultaneously and locally detecting important compounds in neuroscience such as dopamine, serotonin, and adenosine. The Raman results show shifting of the characteristic vibrations of the compounds, observations consistent with previous spectroscopic studies. Although some vibrations are common in these neurotransmitters, Raman mapping was achieved by detecting non-overlapping characteristic spectral signatures of the compounds, as follows: for dopamine the vibration attributed to C-O stretching, for serotonin the indole ring stretching vibration, and for adenosine the adenine ring vibrations. Without damage, dyeing, or preferential sample preparation, confocal Raman mapping provided positive detection of each neurotransmitter, allowing association of the high-resolution spectra with specific micro-scale image regions. Such information is particularly important for complex, heterogeneous samples, where modification of the chemical or physical composition can influence the neurotransmission processes. We also report an estimated dopamine diffusion coefficient two orders of magnitude smaller than that calculated by the flow-injection method.

Vibrational spectroscopic and gravimetric study of some Hofmann-CBA-Type Host and host-guest compounds

International Nuclear Information System (INIS)

Aytekin, M.A.

2005-01-01

In this study, similar to Hofmann type M(C 4 H 7 NH 2 ) 2 Ni(CN) 4 (M=Ni or Co) host and M(C 4 H 7 NH 2 ) 2 Ni(CN) 4 .nG (M=Ni or Co; G=benzene, 1,2-, 1,3-dichlorobenzene; n=the number of guest) hostguest compounds were obtained chemically. The infrared spectra of these compounds were recorded with FT-IR spectrometer in the spectroscopic region of 4000cm-1-400cm-1. From these spectra the vibrational wave numbers of ligand molecule, Ni(CN) 4 2 - ion and guest molecules were determined. The absorption and the liberation processes of the guest molecules in the host compounds were examined at room temperature by gravimetric method. Otherwise, it was seen that the molecular structure was supported by making instrumental analysis of host and some host-guest compounds. By analysing the structures of host and host-guest compounds were found to be similar to those of Hofmann type compounds, ligand molecule cyclobutylamine were coordinated to M metal atom from cyclobutylamine's nitrogen atom, the guest molecules were imprisoned in the structural cavities between the sheets

Correlating the vibrational spectra of structurally related molecules: A spectroscopic measure of similarity.

Science.gov (United States)

Tao, Yunwen; Zou, Wenli; Cremer, Dieter; Kraka, Elfi

2018-03-05

Using catastrophe theory and the concept of a mutation path, an algorithm is developed that leads to the direct correlation of the normal vibrational modes of two structurally related molecules. The mutation path is defined by weighted incremental changes in mass and geometry of the molecules in question, which are successively applied to mutate a molecule into a structurally related molecule and thus continuously converting their normal vibrational spectra from one into the other. Correlation diagrams are generated that accurately relate the normal vibrational modes to each other by utilizing mode-mode overlap criteria and resolving allowed and avoided crossings of vibrational eigenstates. The limitations of normal mode correlation, however, foster the correlation of local vibrational modes, which offer a novel vibrational measure of similarity. It will be shown how this will open new avenues for chemical studies. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Identification of surface species by vibrational normal mode analysis. A DFT study

Science.gov (United States)

Zhao, Zhi-Jian; Genest, Alexander; Rösch, Notker

2017-10-01

Infrared spectroscopy is an important experimental tool for identifying molecular species adsorbed on a metal surface that can be used in situ. Often vibrational modes in such IR spectra of surface species are assigned and identified by comparison with vibrational spectra of related (molecular) compounds of known structure, e. g., an organometallic cluster analogue. To check the validity of this strategy, we carried out a computational study where we compared the normal modes of three C2Hx species (x = 3, 4) in two types of systems, as adsorbates on the Pt(111) surface and as ligands in an organometallic cluster compound. The results of our DFT calculations reproduce the experimental observed frequencies with deviations of at most 50 cm-1. However, the frequencies of the C2Hx species in both types of systems have to be interpreted with due caution if the coordination mode is unknown. The comparative identification strategy works satisfactorily when the coordination mode of the molecular species (ethylidyne) is similar on the surface and in the metal cluster. However, large shifts are encountered when the molecular species (vinyl) exhibits different coordination modes on both types of substrates.

Linearised collective Schroedinger equation for nuclear quadrupole surface vibrations

International Nuclear Information System (INIS)

Greiner, M.; Heumann, D.; Scheid, W.

1990-11-01

The linearisation of the Schroedinger equation for nuclear quadrupole surface vibrations yields a new spin degree of freedom, which is called collective spin and has a value of 3/2. With the introduction of collective spin dependent potentials, this linearised Schroedinger equation is then used for the description of low energy spectra and electromagnetic transition probabilities of some even-odd Xe, Ir and Au nuclei which have a spin 3/2 in their groundstate. (orig.)

Non-spectroscopic surface plasmon sensor with a tunable sensitivity

International Nuclear Information System (INIS)

Wen, Qiuling; Han, Xu; Hu, Chuang; Zhang, Jiasen

2015-01-01

We demonstrate a non-spectroscopic surface plasmon sensor with a tunable sensitivity which is based on the relationship between the wave number of surface plasmon polaritons (SPPs) on metal film and the refractive index of the specimen in contact with the metal film. A change in the wave number of the SPPs results in a variation in the propagation angle of the leakage radiation of the SPPs. A reference light is used to interfere with the leakage radiation, and the refractive index of the specimen can be obtained by measuring the period of the interference fringes. The sensitivity of the sensor can be tuned by changing the incident direction of the reference light and this cannot be realized by conventional surface plasmon sensors. For a reference angle of 1.007°, the sensitivity and resolution of the sensor are 4629 μm/RIU (RIU stands for refractive index unit) and 3.6 × 10 −4 RIU, respectively. In addition, the sensor only needs a monochromatic light source, which simplifies the measurement setup and reduces the cost

Vibrations and spatial patterns in biomimetic surfaces: using the shark-skin effect to control blood clotting.

Science.gov (United States)

Ramachandran, Rahul; Maani, Nazanin; Rayz, Vitaliy L; Nosonovsky, Michael

2016-08-06

We study the effect of small-amplitude fast vibrations and small-amplitude spatial patterns on various systems involving wetting and liquid flow, such as superhydrophobic surfaces, membranes and flow pipes. First, we introduce a mathematical method of averaging the effect of small spatial and temporal patterns and substituting them with an effective force. Such an effective force can change the equilibrium state of a system as well as a phase state, leading to surface texture-induced and vibration-induced phase control. Vibration and patterns can effectively jam holes in vessels with liquid, separate multi-phase flow, change membrane properties, result in propulsion and locomotion and lead to many other multi-scale, nonlinear effects including the shark-skin effect. We discuss the application of such effects to blood flow for novel biomedical 'haemophobic' applications which can prevent blood clotting and thrombosis by controlling the surface pattern at a wall of a vessel (e.g. a catheter or stent).This article is part of the themed issue 'Bioinspired hierarchically structured surfaces for green science'. © 2016 The Author(s).

Nuclear surface vibrations in bag models

International Nuclear Information System (INIS)

Tomio, L.

1984-01-01

The main difficulties found in the hadron bag models are reviewed from the original version of the MIT bag model. Following, with the aim to answer two of the main difficulties in bag models, viz., the parity and the divergence illness, a dynamical model is presented. In the model, the confinement surface of the quarks (bag) is treated like a real physical object which interacts with the quarks and is exposed to vibrations. The model is applied to the nucleon, being observed that his spectrum, in the first excited levels, can be reproduced with resonable precision and obeying to the correct parity order. In the same way that in a similar work of Brown et al., it is observed to be instrumental the inclusion of the effect due to pions. (L.C.) [pt

Analysis of solid-state transformations of pharmaceutical compounds using vibrational spectroscopy

DEFF Research Database (Denmark)

Heinz, Andrea; Strachan, Clare J; Gordon, Keith C

2009-01-01

OBJECTIVES: Solid-state transformations may occur during any stage of pharmaceutical processing and upon storage of a solid dosage form. Early detection and quantification of these transformations during the manufacture of solid dosage forms is important since the physical form of an active...... pharmaceutical ingredient can significantly influence its processing behaviour, including powder flow and compressibility, and biopharmaceutical properties such as solubility, dissolution rate and bioavailability. KEY FINDINGS: Vibrational spectroscopic techniques such as infrared, near-infrared, Raman and, most...... multivariate approaches where even overlapping spectral bands can be analysed. SUMMARY: This review discusses the applications of different vibrational spectroscopic techniques to detect and monitor solid-state transformations possible for crystalline polymorphs, hydrates and amorphous forms of pharmaceutical...

Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

Science.gov (United States)

Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

2016-05-01

The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the л to л* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

Vibrational spectroscopic, structural and nonlinear optical activity studies on 6-aminonicotinamide: A DFT approach

Energy Technology Data Exchange (ETDEWEB)

Asath, R. Mohamed; Premkumar, S.; Mathavan, T.; Benial, A. Milton Franklin, E-mail: miltonfranklin@yahoo.com [Department of Physics, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India); Rekha, T. N. [PG & Research Department of Physics, Lady Doak College, Madurai 625002, Tamilnadu (India); Jawahar, A. [Department of Chemistry, N.M.S.S.V.N College, Madurai-625019, Tamilnadu (India)

2016-05-23

The conformational analysis was carried out for 6-aminonicotinamide (ANA) using potential energy surface scan method and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the related molecular properties were calculated. The ultraviolet-visible spectrum was simulated for both in the gas phase and liquid phase (ethanol) and the π to π* electronic transition was predicted. The nonlinear optical (NLO) activity was studied by means of the first order hyperpolarizability value, which was 8.61 times greater than the urea and the natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ANA molecule is a promising candidate for the NLO materials.

HBr Formation from the Reaction between Gas-phase Bromine Atom and Vibrationally Excited Chemisorbed Hydrogen Atoms on a Si(001)-(2 x 1) Surface

International Nuclear Information System (INIS)

Ree, J.; Yoon, S. H.; Park, K. G.; Kim, Y. H.

2004-01-01

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 x 1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond (vHSi = 0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond

Surface-enhanced raman spectroscopic studies of ellagic acid in silver colloids

Energy Technology Data Exchange (ETDEWEB)

Lee, Seung Jang; Cheong, Byeong Seo; Cho, Han Gook [Dept. of Chemistry, Incheon National University, Incheon (Korea, Republic of)

2015-06-15

Surface-enhanced Raman scattering (SERS) spectroscopy has been applied for the vibrational characterization of ellagic acid (EA), a natural organic dye, using citrate-reduced silver colloids. The infrared and FT-Raman spectra of EA in the solid state were examined for comparison. Spectral assignments of the observed bands were aided by density functional theory (DFT) calculations employing the B3LYP functional. The variations in the SERS spectrum with pH and excitation wavelength were analyzed to gain information on the adsorption- and pH-dependent behaviors of the natural dye on the metal surface. On the basis of the observed spectral features and DFT calculations, the adsorption configuration of EA on the silver metal surface is proposed.

Synthesis, structural characterization, Hirshfeld surface analysis and spectroscopic studies of cadmium (II) chloride complex with 4-hydroxy-1-methylpiperidine

Energy Technology Data Exchange (ETDEWEB)

Soudani, S. [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia); Ferretti, V. [Department of Chemical and Pharmaceutical Sciences and Center for Structural Diffractometry, via Fossato di Mortara 17, I-44121 Ferrara (Italy); Jelsch, C. [CRM2, CNRS, Institut Jean Barriol, Université de Lorraine, Vandoeuvre les Nancy CEDEX (France); Lefebvre, F. [Laboratoire de Chimie Organométallique de Surface (LCOMS), Ecole Supérieure de Chimie Physique Electronique, 69626 Villeurbanne Cedex (France); Nasr, C. Ben, E-mail: cherif_bennasr@yahoo.fr [Université de Carthage, Laboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna (Tunisia)

2016-05-15

The chemical preparation, crystal structure, Hirshfeld surface analysis and spectroscopic characterization of the novel cadmium (II) 4-hydroxy-1-methylpiperidine complex, Cd{sub 4}Cl{sub 10}(C{sub 6}H{sub 14}NO){sub 2}·2H{sub 2}O, have been reported. The atomic arrangement can be described as built up by an anionic framework, formed by edge sharing CdCl{sub 6} and CdCl{sub 5}O octahedral linear chains spreading along the a-axis. These chains are interconnected by water molecules via O–H⋯Cl and O–H⋯O hydrogen bonds to form layers parallel to (011) plane. The organic cations are inserted between layers through C–H⋯Cl hydrogen bonds. Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that the H{sub C}⋯Cl and H{sub C}⋯H{sub C} intermolecular interactions are the most abundant contacts of the organic cation in the crystal packing. The statistical analysis of crystal contacts reveals the driving forces in the packing formation. The {sup 13}C and {sup 15}N CP-MAS NMR spectra are in agreement with the X-ray structure. The vibrational absorption bands were identified by infrared spectroscopy. DFT calculations allowed the attribution of the NMR peaks and of the IR bands.

Conformational and vibrational reassessment of solid paracetamol

Science.gov (United States)

Amado, Ana M.; Azevedo, Celeste; Ribeiro-Claro, Paulo J. A.

2017-08-01

This work provides an answer to the urge for a more detailed and accurate knowledge of the vibrational spectrum of the widely used analgesic/antipyretic drug commonly known as paracetamol. A comprehensive spectroscopic analysis - including infrared, Raman, and inelastic neutron scattering (INS) - is combined with a computational approach which takes account for the effects of intermolecular interactions in the solid state. This allows a full reassessment of the vibrational assignments for Paracetamol, thus preventing the propagation of incorrect data analysis and misassignments already found in the literature. In particular, the vibrational modes involving the hydrogen-bonded Nsbnd H and Osbnd H groups are correctly reallocated to bands shifted by up to 300 cm- 1 relatively to previous assignments.

Force Limited Vibration Test of HESSI Imager

Science.gov (United States)

Amato, Deborah; Pankow, David; Thomsen, Knud

2000-01-01

The High Energy Solar Spectroscopic Imager (HESSI) is a solar x-ray and gamma-ray observatory scheduled for launch in November 2000. Vibration testing of the HESSI imager flight unit was performed in August 1999. The HESSI imager consists of a composite metering tube, two aluminum trays mounted to the tube on titanium flexure mounts, and nine modulation grids mounted on each tray. The vibration tests were acceleration controlled and force limited, in order to prevent overtesting. The force limited strategy reduced the shaker force and notched the acceleration at resonances. The test set-up, test levels, and results are presented. The development of the force limits is also discussed. The imager successfully survived the vibration testing.

Ultrasonic pumping of liquids in the two directions of a vertical tube by a vibrating surface

DEFF Research Database (Denmark)

Santillan, Arturo Orozco; Cutanda Henriquez, Vicente

2010-01-01

of the oscillations of the vibrating horizontal surface determine the direction in which the liquid is pumped. In addition, the size of the gap is also a relevant factor, which has to be significantly small. The carried out numerical simulations show that the Lagrangian excess pressure and the density of linear......It has been reported that it is possible to pump a liquid into the interior of a vertical pipe when its lower end is facing a vibrating plane surface immersed in the liquid. The column of liquid pumped in a thin pipe can be higher than 2 m if the gap between the pipe end and the vibrating...... horizontal surface is very small, around 0.01 mm. In this paper we present experimental results showing that, with a similar set up as the one mentioned above, it is also possible to pump liquids in the opposite direction, from the interior of the pipe through the gap. The general objective of the work has...

The vibrational and buckling behaviors of piezoelectric nanobeams with surface effects

International Nuclear Information System (INIS)

Yan, Z; Jiang, L Y

2011-01-01

In this work, the influence of surface effects, including residual surface stress, surface elasticity and surface piezoelectricity, on the vibrational and buckling behaviors of piezoelectric nanobeams is investigated by using the Euler-Bernoulli beam theory. The surface effects are incorporated by applying the surface piezoelectricity model and the generalized Young-Laplace equations. The results demonstrate that surface effects play a significant role in predicting these behaviors. It is found that the influence of the residual surface stress and the surface piezoelectricity on the resonant frequencies and the critical electric potential for buckling is more prominent than the surface elasticity. The nanobeam boundary conditions are also found to influence the surface effects on these parameters. This study also shows that the resonant frequencies can be tuned by adjusting the applied electrical load. The present study is envisaged to provide useful insights for the design and applications of piezoelectric-beam-based nanodevices.

Structural coloration of metallic surfaces with micro/nano-structures induced by elliptical vibration texturing

Science.gov (United States)

Yang, Yang; Pan, Yayue; Guo, Ping

2017-04-01

Creating orderly periodic micro/nano-structures on metallic surfaces, or structural coloration, for control of surface apparent color and optical reflectivity has been an exciting research topic over the years. The direct applications of structural coloration include color marking, display devices, and invisibility cloak. This paper presents an efficient method to colorize metallic surfaces with periodic micro/nano-gratings using elliptical vibration texturing. When the tool vibration is coupled with a constant cutting velocity, controlled periodic ripples can be generated due to the overlapping tool trajectory. These periodic ripples with a wavelength near visible spectrum can act as micro-gratings to introduce iridescent colors. The proposed technique also provides a flexible method for color marking of metallic surfaces with arbitrary patterns and images by precise control of the spacing distance and orientation of induced micro/nano-ripples. Theoretical analysis and experimental results are given to demonstrate structural coloration of metals by a direct mechanical machining technique.

In situ spectroscopic ellipsometry as a surface sensitive tool to probe thin film growth

International Nuclear Information System (INIS)

Liu, C.

1999-01-01

Sputtered thin film and multilayer x-ray mirrors are made routinely at the Advanced Photon Source (APS) for the APS users. Precise film growth control and characterization are very critical in fabricating high-quality x-ray mirrors. Film thickness calibrations are carried out using in situ and ex situ spectroscopic ellipsometry, interferometry, and x-ray scattering. To better understand the growth and optical properties of different thin film systems, we have carried out a systematic study of sputtered thin films of Au, Rh, Pg Pd, Cu, and Cr, using in situ ellipsometry. Multiple data sets were obtained in situ for each film material with incremental thicknesses and were analyzed with their correlation in mind. We found that in situ spectroscopic ellipsometry as a surface-sensitive tool can also be used to probe the growth and morphology of the thin film system. This application of in situ spectroscopic ellipsometry for metal thin film systems will be discussed

Vibrational and electronic spectra of 2-nitrobenzanthrone: An experimental and computational study

Science.gov (United States)

Onchoke, Kefa K.; Chaudhry, Saad N.; Ojeda, Jorge J.

2016-01-01

The environmental pollutant 2-nitrobenzanthrone (2-NBA) poses human health hazards, and is formed by atmospheric reactions of NOX gases with atmospheric particulates. Though its mutagenic effects have been studied in biological systems, its comprehensive spectroscopic experimental data are scarce. Thus, vibrational and optical spectroscopic analysis (UV-Vis, and fluorescence) of 2-NBA was studied using both experimental and density functional theory employing B3LYP method with 6-311 + G(d,p) basis set. The scaled theoretical vibrational frequencies show good agreement to experiment to within 5 cm- 1 and NBA, respectively. On the basis of normal coordinate analysis complete assignments of harmonic experimental infrared and Raman bands are made. The influence of the nitro group substitution upon the benzanthrone structure and symmetric CH vibrations, and electronic spectra is noted. This study is useful for the development of spectroscopy-mutagenicity relationships in nitrated polycyclic aromatic hydrocarbons.

Use of neutrals backscattering for studying the vibrational properties of solid surfaces

International Nuclear Information System (INIS)

Lapujoulade, J.

1975-01-01

The neutrals (rare gases) elastic scattering may be used for studying some interesting properties of surfaces. However, an analysis of inelastic phenomena is mostly to be performed when vibrational properties of metallic surfaces are investigated. The dispersion relation of surface phonons has not yet been experimentally obtained from neutrals backscattering from solid surfaces, but the quasi-elastic scattering of helium should give this information on condition that velocity measurements are refined in view of directly obtained the distribution function rather than its moments and determining the preponderance of one-phonon transitions, or obtaining a detailed description of many-phonon exchanges [fr

Recent advances in biosynthetic modeling of nitric oxide reductases and insights gained from nuclear resonance vibrational and other spectroscopic studies

Energy Technology Data Exchange (ETDEWEB)

Chakraborty, Saumen; Reed, Julian; Sage, Timothy; Branagan, Nicole C.; Petrik, Igor D.; Miner, Kyle D.; Hu, Michael Y.; Zhao, Jiyong; Alp, E. Ercan; Lu, Yi

2015-10-05

This Forum Article focuses on recent advances in structural and spectroscopic studies of biosynthetic models of nitric oxide reductases (NORs). NORs are complex metalloenzymes found in the denitrification pathway of Earth's nitrogen cycle where they catalyze the proton-dependent twoelectron reduction of nitric oxide (NO) to nitrous oxide (N₂O). While much progress has been made in biochemical and biophysical studies of native NORs and their variants, a. clear mechanistic understanding of this important metalloenzyme related to its function is still elusive. We report herein UV vis and nuclear resonance vibrational spectroscopy (NRVS) studies of mononitrosylated intermediates of the NOR reaction of a biosynthetic model. The ability to selectively substitute metals at either heme or nonheme metal sites allows the introduction of independent ⁵⁷Fe probe atoms at either site, as well as allowing the preparation of analogues of stable reaction intermediates by replacing either metal with a redox inactive metal. Together with previous structural and spectroscopic results, we summarize insights gained from studying these biosynthetic models toward understanding structural features responsible for the NOR activity and its mechanism. As a result, the outlook on NOR modeling is also discussed, with an emphasis on the design of models capable of catalytic turnovers designed based on close mimics of the secondary coordination sphere of native NORs.

Evaluation of Breaking Performance in Vibration-Assisted Electrostatic Surface Induction Actuator

DEFF Research Database (Denmark)

Nemoto, Takeru; Zsurzsan, Tiberiu-Gabriel; Yamamoto, Akio

2015-01-01

This paper evaluates breaking performance of an electrostatic surface induction actuator. The actuator is equipped with piezoelectric vibrator such that the friction between the slider and the stator electrodes can be dramatically reduced by squeeze-film effect. In such an actuator, the friction...... conditions. The result clearly shows the effect of friction change in breaking performance of the actuator....

Polymer Adsorption on Graphite and CVD Graphene Surfaces Studied by Surface-Specific Vibrational Spectroscopy.

Science.gov (United States)

Su, Yudan; Han, Hui-Ling; Cai, Qun; Wu, Qiong; Xie, Mingxiu; Chen, Daoyong; Geng, Baisong; Zhang, Yuanbo; Wang, Feng; Shen, Y R; Tian, Chuanshan

2015-10-14

Sum-frequency vibrational spectroscopy was employed to probe polymer contaminants on chemical vapor deposition (CVD) graphene and to study alkane and polyethylene (PE) adsorption on graphite. In comparing the spectra from the two surfaces, it was found that the contaminants on CVD graphene must be long-chain alkane or PE-like molecules. PE adsorption from solution on the honeycomb surface results in a self-assembled ordered monolayer with the C-C skeleton plane perpendicular to the surface and an adsorption free energy of ∼42 kJ/mol for PE(H(CH2CH2)nH) with n ≈ 60. Such large adsorption energy is responsible for the easy contamination of CVD graphene by impurity in the polymer during standard transfer processes. Contamination can be minimized with the use of purified polymers free of PE-like impurities.

The effect of surface wave propagation on neural responses to vibration in primate glabrous skin.

Directory of Open Access Journals (Sweden)

Louise R Manfredi

Full Text Available Because tactile perception relies on the response of large populations of receptors distributed across the skin, we seek to characterize how a mechanical deformation of the skin at one location affects the skin at another. To this end, we introduce a novel non-contact method to characterize the surface waves produced in the skin under a variety of stimulation conditions. Specifically, we deliver vibrations to the fingertip using a vibratory actuator and measure, using a laser Doppler vibrometer, the surface waves at different distances from the locus of stimulation. First, we show that a vibration applied to the fingertip travels at least the length of the finger and that the rate at which it decays is dependent on stimulus frequency. Furthermore, the resonant frequency of the skin matches the frequency at which a subpopulation of afferents, namely Pacinian afferents, is most sensitive. We show that this skin resonance can lead to a two-fold increase in the strength of the response of a simulated afferent population. Second, the rate at which vibrations propagate across the skin is dependent on the stimulus frequency and plateaus at 7 m/s. The resulting delay in neural activation across locations does not substantially blur the temporal patterning in simulated populations of afferents for frequencies less than 200 Hz, which has important implications about how vibratory frequency is encoded in the responses of somatosensory neurons. Third, we show that, despite the dependence of decay rate and propagation speed on frequency, the waveform of a complex vibration is well preserved as it travels across the skin. Our results suggest, then, that the propagation of surface waves promotes the encoding of spectrally complex vibrations as the entire neural population is exposed to essentially the same stimulus. We also discuss the implications of our results for biomechanical models of the skin.

Raman and infrared spectroscopic studies of the structure of water (H2O, HOD, D2O) in stoichiometric crystalline hydrates and in electrolyte solutions

International Nuclear Information System (INIS)

Buanam-Om, C.

1981-01-01

The chapter of reviews presents in particular the Badger-Bauer-rule, distance and angle dependence of O-H...Y hydrogen bond and the structure of aqueous electrolyte solutions. A chapter of vibrational spectroscopic investigations of crystalline hydrates - metal perchlorate hydrates follows. Two further chapters just so investigate metal halide hydrates and some sulfate hydrates and related systems. The following chapter describes near infrared spectroscopic investigations of HOD(D 2 O) and its electrolyte solutions. The concluding chapter contains thermodynamic consequences and some properties of electrolyte solutions from vibrational spectroscopic investigations. (SPI) [de

An acoustic radiator with integrated cavity and active control of surface vibration

NARCIS (Netherlands)

Berkhoff, Arthur; Tajdari, Farnaz

2017-01-01

This paper presents a method to realize an acoustic source for low frequencies with relatively small thickness. A honeycomb plate structure which is open on one side combines the radiating surface and the major part of the air cavity. The vibration of the plate is controlled with a decentralized

Instrumental analysis of bacterial cells using vibrational and emission Moessbauer spectroscopic techniques

International Nuclear Information System (INIS)

Kamnev, Alexander A.; Tugarova, Anna V.; Antonyuk, Lyudmila P.; Tarantilis, Petros A.; Kulikov, Leonid A.; Perfiliev, Yurii D.; Polissiou, Moschos G.; Gardiner, Philip H.E.

2006-01-01

In biosciences and biotechnology, the expanding application of physicochemical approaches using modern instrumental techniques is an efficient strategy to obtain valuable and often unique information at the molecular level. In this work, we applied a combination of vibrational (Fourier transform infrared (FTIR), FT-Raman) spectroscopic techniques, useful in overall structural and compositional analysis of bacterial cells of the rhizobacterium Azospirillum brasilense, with 57 Co emission Moessbauer spectroscopy (EMS) used for sensitive monitoring of metal binding and further transformations in live bacterial cells. The information obtained, together with ICP-MS analyses for metals taken up by the bacteria, is useful in analysing the impact of the environmental conditions (heavy metal stress) on the bacterial metabolism and some differences in the heavy metal stress-induced behaviour of non-endophytic (Sp7) and facultatively endophytic (Sp245) strains. The results show that, while both strains Sp7 and Sp245 take up noticeable and comparable amounts of heavy metals from the medium (0.12 and 0.13 mg Co, 0.48 and 0.44 mg Cu or 4.2 and 2.1 mg Zn per gram of dry biomass, respectively, at a metal concentration of 0.2 mM in the medium), their metabolic responses differ essentially. Whereas for strain Sp7 the FTIR measurements showed significant accumulation of polyhydroxyalkanoates as storage materials involved in stress endurance, strain Sp245 did not show any major changes in cellular composition. Nevertheless, EMS measurements showed rapid binding of cobalt(II) by live bacterial cells (chemically similar to metal binding by dead bacteria) and its further transformation in the live cells within an hour

Instrumental analysis of bacterial cells using vibrational and emission Moessbauer spectroscopic techniques

Energy Technology Data Exchange (ETDEWEB)

Kamnev, Alexander A. [Laboratory of Biochemistry of Plant-Bacterial Symbioses, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov (Russian Federation)]. E-mail: aakamnev@ibppm.sgu.ru; Tugarova, Anna V. [Laboratory of Biochemistry of Plant-Bacterial Symbioses, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov (Russian Federation); Antonyuk, Lyudmila P. [Laboratory of Biochemistry of Plant-Bacterial Symbioses, Institute of Biochemistry and Physiology of Plants and Microorganisms, Russian Academy of Sciences, 410049 Saratov (Russian Federation); Tarantilis, Petros A. [Laboratory of Chemistry, Department of Science, Agricultural University of Athens, 11855 Athens (Greece); Kulikov, Leonid A. [Laboratory of Nuclear Chemistry Techniques, Department of Radiochemistry, Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Perfiliev, Yurii D. [Laboratory of Nuclear Chemistry Techniques, Department of Radiochemistry, Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Polissiou, Moschos G. [Laboratory of Chemistry, Department of Science, Agricultural University of Athens, 11855 Athens (Greece); Gardiner, Philip H.E. [Division of Chemistry, School of Science and Mathematics, Sheffield Hallam University, Sheffield S1 1WB (United Kingdom)

2006-07-28

In biosciences and biotechnology, the expanding application of physicochemical approaches using modern instrumental techniques is an efficient strategy to obtain valuable and often unique information at the molecular level. In this work, we applied a combination of vibrational (Fourier transform infrared (FTIR), FT-Raman) spectroscopic techniques, useful in overall structural and compositional analysis of bacterial cells of the rhizobacterium Azospirillum brasilense, with {sup 57}Co emission Moessbauer spectroscopy (EMS) used for sensitive monitoring of metal binding and further transformations in live bacterial cells. The information obtained, together with ICP-MS analyses for metals taken up by the bacteria, is useful in analysing the impact of the environmental conditions (heavy metal stress) on the bacterial metabolism and some differences in the heavy metal stress-induced behaviour of non-endophytic (Sp7) and facultatively endophytic (Sp245) strains. The results show that, while both strains Sp7 and Sp245 take up noticeable and comparable amounts of heavy metals from the medium (0.12 and 0.13 mg Co, 0.48 and 0.44 mg Cu or 4.2 and 2.1 mg Zn per gram of dry biomass, respectively, at a metal concentration of 0.2 mM in the medium), their metabolic responses differ essentially. Whereas for strain Sp7 the FTIR measurements showed significant accumulation of polyhydroxyalkanoates as storage materials involved in stress endurance, strain Sp245 did not show any major changes in cellular composition. Nevertheless, EMS measurements showed rapid binding of cobalt(II) by live bacterial cells (chemically similar to metal binding by dead bacteria) and its further transformation in the live cells within an hour.

Recovering Intrinsic Fragmental Vibrations Using the Generalized Subsystem Vibrational Analysis.

Science.gov (United States)

Tao, Yunwen; Tian, Chuan; Verma, Niraj; Zou, Wenli; Wang, Chao; Cremer, Dieter; Kraka, Elfi

2018-05-08

Normal vibrational modes are generally delocalized over the molecular system, which makes it difficult to assign certain vibrations to specific fragments or functional groups. We introduce a new approach, the Generalized Subsystem Vibrational Analysis (GSVA), to extract the intrinsic fragmental vibrations of any fragment/subsystem from the whole system via the evaluation of the corresponding effective Hessian matrix. The retention of the curvature information with regard to the potential energy surface for the effective Hessian matrix endows our approach with a concrete physical basis and enables the normal vibrational modes of different molecular systems to be legitimately comparable. Furthermore, the intrinsic fragmental vibrations act as a new link between the Konkoli-Cremer local vibrational modes and the normal vibrational modes.

Accurate potential energy curves, spectroscopic parameters, transition dipole moments, and transition probabilities of 21 low-lying states of the CO+ cation

Science.gov (United States)

Xing, Wei; Shi, Deheng; Zhang, Jicai; Sun, Jinfeng; Zhu, Zunlue

2018-05-01

This paper calculates the potential energy curves of 21 Λ-S and 42 Ω states, which arise from the first two dissociation asymptotes of the CO+ cation. The calculations are conducted using the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with the Davidson correction. To improve the reliability and accuracy of the potential energy curves, core-valence correlation and scalar relativistic corrections, as well as the extrapolation of potential energies to the complete basis set limit are taken into account. The spectroscopic parameters and vibrational levels are determined. The spin-orbit coupling effect on the spectroscopic parameters and vibrational levels is evaluated. To better study the transition probabilities, the transition dipole moments are computed. The Franck-Condon factors and Einstein coefficients of some emissions are calculated. The radiative lifetimes are determined for a number of vibrational levels of several states. The transitions between different Λ-S states are evaluated. Spectroscopic routines for observing these states are proposed. The spectroscopic parameters, vibrational levels, transition dipole moments, and transition probabilities reported in this paper can be considered to be very reliable and can be used as guidelines for detecting these states in an appropriate spectroscopy experiment, especially for the states that were very difficult to observe or were not detected in previous experiments.

Application of the wavelet packet transform to vibration signals for surface roughness monitoring in CNC turning operations

Science.gov (United States)

García Plaza, E.; Núñez López, P. J.

2018-01-01

The wavelet packet transform method decomposes a time signal into several independent time-frequency signals called packets. This enables the temporary location of transient events occurring during the monitoring of the cutting processes, which is advantageous in monitoring condition and fault diagnosis. This paper proposes the monitoring of surface roughness using a single low cost sensor that is easily implemented in numerical control machine tools in order to make on-line decisions on workpiece surface finish quality. Packet feature extraction in vibration signals was applied to correlate the sensor signals to measured surface roughness. For the successful application of the WPT method, mother wavelets, packet decomposition level, and appropriate packet selection methods should be considered, but are poorly understood aspects in the literature. In this novel contribution, forty mother wavelets, optimal decomposition level, and packet reduction methods were analysed, as well as identifying the effective frequency range providing the best packet feature extraction for monitoring surface finish. The results show that mother wavelet biorthogonal 4.4 in decomposition level L3 with the fusion of the orthogonal vibration components (ax + ay + az) were the best option in the vibration signal and surface roughness correlation. The best packets were found in the medium-high frequency DDA (6250-9375 Hz) and high frequency ADA (9375-12500 Hz) ranges, and the feed acceleration component ay was the primary source of information. The packet reduction methods forfeited packets with relevant features to the signal, leading to poor results for the prediction of surface roughness. WPT is a robust vibration signal processing method for the monitoring of surface roughness using a single sensor without other information sources, satisfactory results were obtained in comparison to other processing methods with a low computational cost.

Large Amplitude Motions in Polyatomic Molecule Spectra: Intramolecular Vibrational Redistribution and Isomerization

National Research Council Canada - National Science Library

Field, Robert

1997-01-01

Through Stimulated Emission Pumping (SEP) studies of highly excited vibrational levels of the electronic ground state of HCP, the spectroscopic signatures of bond breaking isomer/atom (HCP right arrow HPC...

Linear response properties required to simulate vibrational spectra of biomolecules in various media: (R)-phenyloxirane (A comparative theoretical and spectroscopic vibrational study)

DEFF Research Database (Denmark)

Jalkanen, Karl J.; Jürgensen, Vibeke Würtz; Degtyarenko, I.M.

2005-01-01

We here present a combined VA, VCD, Raman and ROA vibrational study of phenyloxirane. We have simulated the vibrational absorption (VA), also called IR, vibrational circular dichroism (VCD), Raman scattering and Raman optical activity (ROA) intensities utilizing the density functional theory (DFT...

Vibrational properties of homopolar and heteropolar surfaces and interfaces of the CdTe/HgTe system

International Nuclear Information System (INIS)

Rey Gonzalez, R.; Camacho B, A.; Quiroga, L.

1993-08-01

We present results of calculations for the density of vibrational modes for (001) and (111) homopolar, as well as for (011) heteropolar free surfaces of CdTe and HgTe. A rigid-ion model with a dynamical matrix parametrization including force constants up to second neighbours is used. We report on the existence of highly localized surface resonant modes at the top of the acoustic branch for CdTe and the bottom of the optical branch for HgTe. A different behaviour in the three directions analysed is found. The interface atomic planes show themselves as phonon gapless layers. The contribution of in-plane and out-of-plane vibration is analysed for both the surface and interface cases. (author). 7 refs, 7 figs

Vibrational spectroscopic characterisation of salmeterol xinafoate polymorphs and a preliminary investigation of their transformation using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry

International Nuclear Information System (INIS)

Ali, Hassan Refat H.; Edwards, Howell G.M.; Hargreaves, Michael D.; Munshi, Tasnim; Scowen, Ian J.; Telford, Richard J.

2008-01-01

Knowledge and control of the polymorphic phases of chemical compounds are important aspects of drug development in the pharmaceutical industry. Salmeterol xinafoate, a long acting β-adrenergic receptor agonist, exists in two polymorphic Forms, I and II. Raman and near infrared spectra were obtained of these polymorphs at selected wavelengths in the range of 488-1064 nm; significant differences in the Raman and near-infrared spectra were apparent and key spectral marker bands have been identified for the vibrational spectroscopic characterisation of the individual polymorphs which were also characterised with X ray diffractometry. The solid-state transition of salmeterol xinafoate polymorphs was studied using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry isothermally between transitions. This method assisted in the unambiguous characterisation of the two polymorphic forms by providing a simultaneous probe of both the thermal and vibrational data. The study demonstrates the value of a rapid in situ analysis of a drug polymorph which can be of potential value for at-line in-process control

Vibrational spectroscopic characterisation of salmeterol xinafoate polymorphs and a preliminary investigation of their transformation using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry

Energy Technology Data Exchange (ETDEWEB)

Ali, Hassan Refat H. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom); Edwards, Howell G.M. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom)], E-mail: H.G.M.Edwards@bradford.ac.uk; Hargreaves, Michael D.; Munshi, Tasnim; Scowen, Ian J.; Telford, Richard J. [Chemical and Forensic Sciences/University Analytical Centre, School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP (United Kingdom)

2008-07-14

Knowledge and control of the polymorphic phases of chemical compounds are important aspects of drug development in the pharmaceutical industry. Salmeterol xinafoate, a long acting {beta}-adrenergic receptor agonist, exists in two polymorphic Forms, I and II. Raman and near infrared spectra were obtained of these polymorphs at selected wavelengths in the range of 488-1064 nm; significant differences in the Raman and near-infrared spectra were apparent and key spectral marker bands have been identified for the vibrational spectroscopic characterisation of the individual polymorphs which were also characterised with X ray diffractometry. The solid-state transition of salmeterol xinafoate polymorphs was studied using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry isothermally between transitions. This method assisted in the unambiguous characterisation of the two polymorphic forms by providing a simultaneous probe of both the thermal and vibrational data. The study demonstrates the value of a rapid in situ analysis of a drug polymorph which can be of potential value for at-line in-process control.

Vibrational spectroscopic study of poldervaartite CaCa[SiO3(OH)(OH)

Science.gov (United States)

Frost, Ray L.; López, Andrés; Scholz, Ricardo; Lima, Rosa Malena Fernandes

2015-02-01

We have studied the mineral poldervaartite CaCa[SiO3(OH)(OH)] which forms a series with its manganese analogue olmiite CaMn[SiO3(OH)](OH) using a range of techniques including scanning electron microscopy, thermogravimetric analysis, Raman and infrared spectroscopy. Chemical analysis shows the mineral is reasonably pure and contains only calcium and manganese with low amounts of Al and F. Thermogravimetric analysis proves the mineral decomposes at 485 °C with a mass loss of 7.6% compared with the theoretical mass loss of 7.7%. A strong Raman band at 852 cm-1 is assigned to the SiO stretching vibration of the SiO3(OH) units. Two Raman bands at 914 and 953 cm-1 are attributed to the antisymmetric vibrations. Intense prominent peaks observed at 3487, 3502, 3509, 3521 and 3547 cm-1 are assigned to the OH stretching vibration of the SiO3(OH) units. The observation of multiple OH bands supports the concept of the non-equivalence of the OH units. Vibrational spectroscopy enables a detailed assessment of the molecular structure of poldervaartite.

Vibration mixer

Energy Technology Data Exchange (ETDEWEB)

Alekhin, S.A.; Chernov, V.S.; Denisenko, V.V.; Gorodnyanskiy, I.F.; Prokopov, L.I.; Tikhonov, Yu.P.

1983-01-01

The vibration mixer is proposed which contains a housing, vibration drive with rod installed in the upper part of the mixing mechanism made in the form of a hollow shaft with blades. In order to improve intensity of mixing and dispersion of the mud, the shaft with the blades is arranged on the rod of the vibrator and is equipped with a cam coupling whose drive disc is attached to the vibration rod. The rod is made helical, while the drive disc of the cam coupling is attached to the helical surface of the rod. In addition, the vibration mixer is equipped with perforated discs installed on the ends of the rods.

The effect of synthesis temperature on the formation of hydrotalcites in Bayer liquor: a vibrational spectroscopic analysis.

Science.gov (United States)

Palmer, Sara J; Frost, Ray L

2009-07-01

The seawater neutralization process is currently used in the alumina industry to reduce the pH and dissolved metal concentrations in bauxite refinery residues through the precipitation of Mg, Al, and Ca hydroxide and carbonate minerals. This neutralization method is very similar to the co-precipitation method used to synthesize hydrotalcite (Mg6Al2(OH)16CO3.4H2O). This study looks at the effect of temperature on the type of precipitates that form from the seawater neutralization process of Bayer liquor. The Bayer precipitates have been characterized by a variety of techniques, including X-ray diffraction (XRD), Raman spectroscopy, and infrared spectroscopy. The mineralogical composition of Bayer precipitates largely includes hydrotalcite, hydromagnesite, and calcium carbonate species. Analysis with XRD determined that Bayer hydrotalcites that are synthesized at 55 degrees C have a larger interlayer distance, indicating that more anions are removed from Bayer liquor. Vibrational spectroscopic techniques have identified an increase in hydrogen bond strength for precipitates formed at 55 degrees C, suggesting the formation of a more stable Bayer hydrotalcite. Raman spectroscopy identified the intercalation of sulfate and carbonate anions into Bayer hydrotalcites using these synthesis conditions.

Vibrational spectroscopy of SnBr4 and CCl4 using Lie algebraic ...

Indian Academy of Sciences (India)

experimentalists because of the development of new laser spectroscopic techniques. Wulfman played a ... used Lie algebraic methods to study the spectra of molecules (vibron model) using. U(4) algebra. ..... to vibrations of gas molecules.

Conformational, structural, vibrational and quantum chemical analysis on 4-aminobenzohydrazide and 4-hydroxybenzohydrazide--a comparative study.

Science.gov (United States)

Arjunan, V; Jayaprakash, A; Carthigayan, K; Periandy, S; Mohan, S

2013-05-01

Experimental and theoretical quantum chemical studies were carried out on 4-hydroxybenzohydrazide (4HBH) and 4-aminobenzohydrazide (4ABH) using FTIR and FT-Raman spectral data. The structural characteristics and vibrational spectroscopic analysis were carried performed by quantum chemical methods with the hybrid exchange-correlation functional B3LYP using 6-31G(**), 6-311++G(**) and aug-cc-pVDZ basis sets. The most stable conformer of the title compounds have been determined from the analysis of potential energy surface. The stable molecular geometries, electronic and thermodynamic parameters, IR intensities, harmonic vibrational frequencies, depolarisation ratio and Raman intensities have been computed. Molecular electrostatic potential and frontier molecular orbitals were constructed to understand the electronic properties. The potential energy distributions (PEDs) were calculated to explain the mixing of fundamental modes. The theoretical geometrical parameters and the fundamental frequencies were compared with the experimental. The interactions of hydroxy and amino group substitutions on the characteristic vibrations of the ring and hydrazide group have been analysed. Copyright © 2013 Elsevier B.V. All rights reserved.

FTIR Emission spectroscopy of surfaces

Science.gov (United States)

Van Woerkom, P. C. M.

A number of vibrational spectroscopic techniques are available For the study of surfaces, such as ATR, IR reflection-absorption, IR emission, etc. Infrared emission is hardly used, although interesting applications are possible now due to the high sensitivity of Fourier transform IR (FTIR) spectrometers. Two examples, where infrared emission measurements are very fruitful, will be given. One is the investigation of the curing behaviour of organic coatings, the other is the in situ study of heterogeneously catalyzed reactions. Undoubtedly, infrared emission measurements offer a number of specific advantages in some cases. Especially the less critical demands on the sample preparation are important.

Theoretical study of sum-frequency vibrational spectroscopy on limonene surface

International Nuclear Information System (INIS)

Zheng, Ren-Hui; Liu, Hao; Jing, Yuan-Yuan; Wang, Bo-Yang; Shi, Qiang; Wei, Wen-Mei

2014-01-01

By combining molecule dynamics (MD) simulation and quantum chemistry computation, we calculate the surface sum-frequency vibrational spectroscopy (SFVS) of R-limonene molecules at the gas-liquid interface for SSP, PPP, and SPS polarization combinations. The distributions of the Euler angles are obtained using MD simulation, the ψ-distribution is between isotropic and Gaussian. Instead of the MD distributions, different analytical distributions such as the δ-function, Gaussian and isotropic distributions are applied to simulate surface SFVS. We find that different distributions significantly affect the absolute SFVS intensity and also influence on relative SFVS intensity, and the δ-function distribution should be used with caution when the orientation distribution is broad. Furthermore, the reason that the SPS signal is weak in reflected arrangement is discussed

Theoretical study of sum-frequency vibrational spectroscopy on limonene surface

Energy Technology Data Exchange (ETDEWEB)

Zheng, Ren-Hui, E-mail: zrh@iccas.ac.cn; Liu, Hao; Jing, Yuan-Yuan; Wang, Bo-Yang; Shi, Qiang [Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Zhongguancun, Beijing 100190 (China); Wei, Wen-Mei [Department of Chemistry, College of Basic Medicine, Anhui Medical University, Hefei, Anhui 230032 (China)

2014-03-14

By combining molecule dynamics (MD) simulation and quantum chemistry computation, we calculate the surface sum-frequency vibrational spectroscopy (SFVS) of R-limonene molecules at the gas-liquid interface for SSP, PPP, and SPS polarization combinations. The distributions of the Euler angles are obtained using MD simulation, the ψ-distribution is between isotropic and Gaussian. Instead of the MD distributions, different analytical distributions such as the δ-function, Gaussian and isotropic distributions are applied to simulate surface SFVS. We find that different distributions significantly affect the absolute SFVS intensity and also influence on relative SFVS intensity, and the δ-function distribution should be used with caution when the orientation distribution is broad. Furthermore, the reason that the SPS signal is weak in reflected arrangement is discussed.

Effects of surface topography and vibrations on wetting: Superhydrophobicity, icephobicity and corrosion resistance

Science.gov (United States)

Ramachandran, Rahul

Concrete and metallic materials are widely used in construction and water industry. The interaction of both these materials with water and ice (or snow) produces undesirable results and is therefore of interest. Water that gets absorbed into the pores of dry concrete expands on freezing and can lead to crack formation. Also, the ice accretion on concrete surfaces such as roadways can have disastrous consequence. Metallic components used in the water industry undergo corrosion due to contact with aqueous corrosive solutions. Therefore, it is desirable to make concrete water/ice-repellent, and to make metallic surfaces corrosion-resistant. Recent advances in micro/nanotechnology have made it possible to design functional micro/nanostructured surfaces with micro/nanotopography providing low adhesion. Some examples of such surfaces are superhydrophobic surfaces, which are extremely water repellent, and icephobic surfaces, which have low ice adhesion, repel incoming water droplets before freezing, or delay ice nucleation. This dissertation investigates the effects of surface micro/nanotopography and small amplitude fast vibrations on the wetting and adhesion of concrete with the goal of producing hydrophobic and icephobic concrete, and on the wetting of metallic surfaces to prevent corrosion. The relationship between surface micro/nanotopography and small fast vibrations is established using the method of separation of motions. Both these small scale effects can be substituted by an effective force or energy. The structure-property relationships in materials and surfaces are established. Both vibrations as well as surface micro/nanopatterns can affect wetting properties such as contact angle and surface free energy. Hydrophobic engineered cementitious composite samples are produced by controlling their surface topography and surface free energy. The surface topography is controlled by varying the concrete mixture composition. The surface free energy of concrete is

Mitigating ground vibration by periodic inclusions and surface structures

DEFF Research Database (Denmark)

Andersen, Lars Vabbersgaard; Bucinskas, Paulius; Persson, Peter

2016-01-01

Ground vibration from traffic is a source of nuisance in urbanized areas. Trenches and wave barriers can provide mitigation of vibrations, but single barriers need to have a large depth to be effective-especially in the low-frequency range relevant to traffic-induced vibration. Alternatively...

Transformation of potential energy surfaces for estimating isotopic shifts in anharmonic vibrational frequency calculations

Energy Technology Data Exchange (ETDEWEB)

Meier, Patrick; Oschetzki, Dominik; Rauhut, Guntram, E-mail: rauhut@theochem.uni-stuttgart.de [Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart (Germany); Berger, Robert [Clemens-Schöpf Institut für Organische Chemie and Biochemie, Technische Universität Darmstadt, Petersenstrasse 22, 64287 Darmstadt (Germany)

2014-05-14

A transformation of potential energy surfaces (PES) being represented by multi-mode expansions is introduced, which allows for the calculation of anharmonic vibrational spectra of any isotopologue from a single PES. This simplifies the analysis of infrared spectra due to significant CPU-time savings. An investigation of remaining deviations due to truncations and the so-called multi-level approximation is provided. The importance of vibrational-rotational couplings for small molecules is discussed in detail. In addition, an analysis is proposed, which provides information about the quality of the transformation prior to its execution. Benchmark calculations are provided for a set of small molecules.

Proceedings of the national conference on exploring the frontiers of vibrational spectroscopy: abstracts

International Nuclear Information System (INIS)

2011-01-01

Spectroscopy has played and is playing a very important role as it is one of the most efficient methods of molecular structure studies with the help of which direct information about the chemical compounds can be obtained. Spectroscopy has its contribution in a number of branches in areas such as medicine, industry, environment, agriculture, power, construction, forensic analysis (both criminal and civil cases), etc., where it has revolutionized the very face of these sectors. Vibrational spectroscopic (Infrared and Raman) techniques have demonstrated potential to provide non-destructive, rapid clinically relevant diagnostic information. Raman and infrared spectroscopy enable the biochemical signatures from biological tissues to be extracted and analyzed there by advancing the treatment of cancer. Advancement in instrumentation has allowed the development of numerous infrared and Raman spectroscopic methods. Infrared spectroscopy is tremendously used in the fields of pharmaceuticals. medical diagnostics food and agrochemical quality control, and combustion research. Raman spectroscopy is used in condensed matter physics, biomedicinal fields for tissue analysis and chemistry to study vibrational, rotational, and other low-frequency modes in a system. Keeping in mind the fast development: in the Spectroscopy, we have planned to organize a national level conference for 2 days on 'Exploring the Frontiers of Vibrational Spectroscopy' to bring out the tremendous potential of various Spectroscopic techniques available at the global level. Papers relevant to INIS are indexed separately

Structural, vibrational spectroscopic and nonlinear optical activity studies on 2-hydroxy- 3, 5-dinitropyridine: A DFT approach

Science.gov (United States)

Asath, R. Mohamed; Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

2015-06-01

The conformational analysis was carried out for 2-Hydroxy- 3, 5-dinitropyridine molecule using potential energy surface scan and the most stable optimized conformer was predicted. The vibrational frequencies and Mulliken atomic charge distribution were calculated for the optimized geometry of the molecule using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intramolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness values of the title molecule were carried out. The nonlinear optical activity of the molecule was studied by means of first order hyperpolarizability, which was computed as 7.64 times greater than urea. The natural bond orbital analysis was performed to confirm the nonlinear optical activity of the molecule.

State-to-state inelastic and reactive molecular beam scattering from surfaces

International Nuclear Information System (INIS)

Lykke, K.R.; Kay, B.D.

1990-01-01

Resonantly enhanced multiphoton ionization (REMPI) laser spectroscopic and molecular beam-surface scattering techniques are coupled to study inelastic and reactive gas-surface scattering with state-to-state specificity. Rotational, vibrational, translational and angular distributions have been measured for the inelastic scattering of HCI and N 2 from Au(111). In both cases the scattering is direct-inelastic in nature and exhibits interesting dynamical features such as rotational rainbow scattering. In an effort to elucidate the dynamics of chemical reactions occurring on surfaces we have extended our quantum-resolved scattering studies to include the reactive scattering of a beam of gas phase H-atoms from a chlorinated metal surface M-CI. The nascent rotational and vibrational distributions of the HCI product are determined using REMPI. The thermochemistry for this reaction on Au indicates that the product formation proceeding through chemisorbed H-atoms is slightly endothermic while direct reaction of a has phase H-atom with M-CI is highly exothermic (ca. 50 kcal/mole). Details of the experimental techniques, results and implications regarding the scattering dynamics are discussed. 55 ref., 8 fig

Vibrational spectroscopic study of cationic phosphorus dendrimers with aminoethylpiperidine terminal groups

Science.gov (United States)

Furer, V. L.; Vandyukov, A. E.; Tripathi, V.; Majoral, J. P.; Caminade, A. M.; Kovalenko, V. I.

2018-04-01

Two generations of phosphoric dendrimers with piperidine functional groups were synthesized for use in biology and medicine. Neutral samples are soluble in organic solvents but after protonation these dendrimers become water soluble and can be used for biological experiments. The FTIR and FT Raman spectra of two generations of dendrimers Gi constructed from the cyclotriphosphazene core, repeating units sbnd Osbnd C6H4sbnd CHdbnd Nsbnd N(CH3)sbnd P(S)molecular structure and vibrational spectra of the first generation dendrimer was performed by the method of DFT. This molecule has flat, repeating units and a plane of symmetry passing through the core. The calculation of the distribution of potential energy made it possible to classify the bands in the experimental spectra of dendrimers. Amine groups are manifested in the form of a band of NH stretching vibrations at 3389 cm-1 in the IR spectrum of G1. NH+ stretching bands located at 2646 and 2540 cm-1 in the IR spectrum of G2. The stretching vibrations of NH+ groups are noticeably shifted to low frequencies due to the formation of a hydrogen bond with the chlorine atom. The line at 1575 cm-1 in the Raman spectrum of G1 is characteristic for repeating units.

Theory for Nonlinear Spectroscopy of Vibrational Polaritons

OpenAIRE

Ribeiro, RF; Dunkelberger, AD; Xiang, B; Xiong, W; Simpkins, BS; Owrutsky, JC; Yuen-Zhou, J

2017-01-01

Molecular polaritons have gained considerable attention due to their potential to control nanoscale molecular processes by harnessing electromagnetic coherence. Although recent experiments with liquid-phase vibrational polaritons have shown great promise for exploiting these effects, significant challenges remain in interpreting their spectroscopic signatures. In this letter, we develop a quantum-mechanical theory of pump-probe spectroscopy for this class of polaritons based on the quantum La...

Anharmonic vibrational spectroscopic investigation of malonaldehyde

International Nuclear Information System (INIS)

Alparone, A.; Millefiori, S.

2003-01-01

Anharmonic IR spectra of H-bonded and non-H-bonded conformers of malonaldehyde (MA) and its isotopomers MA-D 6 D 8 and MA-D 7 D 9 have been computed by the Vibrational-Self-Consistent-Field (VSCF) and the correlation-corrected-VSCF (CC-VSCF) techniques using ab initio MP2/6-31G*(+p) potential energies. The agreement between the experimental and calculated frequencies is significantly improved to within 2-3%. Anharmonic contributions are substantial especially for νOH of the H-bonded form, by reducing the harmonic value by more than 500 cm -1 . The effect is less important in the non-H-bonded form. The νOH stretching mode is strongly coupled with the ν 3 mode (essentially νCH 7 ) and with the in-plane and out-of-plane OH bending deformations. H-bond formation and deuteration batochromically shift νOH by an amount which is influenced by the anharmonic terms, the major contribution arising from coupling between modes. The comparison with the νOH mode of some other H-bonded systems suggests that anharmonic correction follows H-bonding strength

Interaction of low energy electrons with surface lattice vibrations. Final report

International Nuclear Information System (INIS)

Tong, S.Y.

1984-01-01

In carrying out the DOE contract, we have succeeded in constructing a new microscopic theory, with multiple scattering, for the inelastic scattering of electrons by surface vibrations. We have applied the theory to detailed studies of angle and energy variations of the inelastic cross-section for two important systems in surface physics: carbon monoxide molecules adsorbed on the (100) surface of a nickel crystal, and hydrogen atoms adsorbed on a reconstructed tungsten (100) surface. These calculations have outlined general trends that we expect to apply to a wide variety of systems. Also, we have discovered a series of new selection rules that apply to off-specular scattering. Particularly interesting are pseudo-selection rules which are not group theoretical in origin, but approximate statements that hold well when the electron scattering amplitude exhibits a slow energy variation. We have found and defined conditions for which these selection rules would hold and break down

Application of comparative vibrational spectroscopic and mechanistic studies in analysis of fisetin structure

Science.gov (United States)

Dimitrić Marković, Jasmina M.; Marković, Zoran S.; Milenković, Dejan; Jeremić, Svetlana

2011-12-01

This paper addresses experimental and theoretical research in fisetin (2-(3,4-dihydroxyphenyl)-3,7-dihydroxychromen-4-one) structure by means of experimental IR and Raman spectroscopies and mechanistic calculations. Density Functional Theory calculations, with M05-2X functional and the 6-311+G (2df, p) basis set implemented in the Gaussian 09 package, are performed with the aim to support molecular structure, vibrational bands' positions and their intensities. Potential energy distribution (PED) values and the description of the largest vibrational contributions to the normal modes are calculated. The most intense bands appear in the 1650-1500 cm -1 wavenumber region. This region involves a combination of the C dbnd O, C2 dbnd C3 and C-C stretching vibrational modes. Most of the bands in the 1500-1000 cm -1 range involve C-C stretching, O-C stretching and in-plane C-C-H, C-O-H, C-C-O and C-C-C bending vibrations of the rings. The region below 1000 cm -1 is characteristic to the combination of in plane C-C-C-H, H-C-C-H, C-C-C-C, C-C-O-C and out of plane O-C-C-C, C-C-O-C, C-C-C-C torsional modes. The Raman spectra of baicalein and quercetin were used for qualitative comparison with fisetin spectrum and verification of band assignments. The applied detailed vibrational spectral analysis and the assignments of the bands, proposed on the basis of fundamentals, reproduced the experimental results with high degree of accuracy.

Optical spectroscopic elucidation of beta-turns in disulfide bridged cyclic tetrapeptides.

Science.gov (United States)

Borics, Attila; Murphy, Richard F; Lovas, Sándor

2007-01-01

Vibrational circular dichroism (VCD) spectroscopic features of type II beta-turns were characterized previously, but, criteria for differentiation between beta-turn types had not been established yet. Model tetrapeptides, cyclized through a disulfide bridge, were designed on the basis of previous experimental results and the observed incidence of amino acid residues in the i + 1 and i + 2 positions in beta-turns, to determine the features of VCD spectra of type I and II beta-turns. The results were correlated with electronic circular dichroism (ECD) spectra and VCD spectra calculated from conformational data obtained by molecular dynamics (MD) simulations. All cyclic tetrapeptides yielded VCD signals with a higher frequency negative and a lower frequency positive couplet with negative lobes overlapping. MD simulations confirmed the conformational homogeneity of these peptides in solution. Comparison with ECD spectroscopy, MD, and quantum chemical calculation results suggested that the low frequency component of VCD spectra originating from the tertiary amide vibrations could be used to distinguish between types of beta-turn structures. On the basis of this observation, VCD spectroscopic features of type II and VIII beta-turns and ECD spectroscopic properties of a type VIII beta-turn were suggested. The need for independent experimental as well as theoretical investigations to obtain decisive conformational information was recognized. Copyright 2006 Wiley Periodicals, Inc.

The Astrophysical Weeds: Rotational Transitions in Excited Vibrational States

Science.gov (United States)

Alonso, José L.; Kolesniková, Lucie; Alonso, Elena R.; Mata, Santiago

2017-06-01

The number of unidentified lines in the millimeter and submillimeter wave surveys of the interstellar medium has grown rapidly. The major contributions are due to rotational transitions in excited vibrational states of a relatively few molecules that are called the astrophysical weeds. necessary data to deal with spectral lines from astrophysical weeds species can be obtained from detailed laboratory rotational measurements in the microwave and millimeter wave region. A general procedure is being used at Valladolid combining different time and/or frequency domain spectroscopic tools of varying importance for providing the precise set of spectroscopic constants that could be used to search for this species in the ISM. This is illustrated in the present contribution through its application to several significant examples. Fortman, S. M., Medvedev, I. R., Neese, C.F., & De Lucia, F.C. 2010, ApJ,725, 1682 Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile, L. Kolesniková, E. R. Alonso, S. Mata, and J. L. Alonso, The Astrophysical Journal Supplement Series 2017, (in press).

Effect of flask vibration time on casting integrity, Surface Penetration and Coating Inclusion in lost foam casting of Al-Si Alloy

International Nuclear Information System (INIS)

Karimian, Majid; Idris, M. H.; Ourdjini, A.; Muthu, Kali

2011-01-01

The paper presents the result of an experimental investigation conducted on medium aluminum silicon alloy casting- LM6, using no-vacuum assisted lost foam casting process. The study is directed for establishing the relationship between the flask vibrations times developed for molded sample on the casting integrity, surface penetration and coating inclusion defects of the casting. Four different flask vibration times namely 180, 120, 90 and 60 sec. were investigated. The casting integrity was investigated in terms of fulfilling in all portions and edges. The surface penetration was measured using optical microscope whilst image analyzer was used to quantify the percentage of coating inclusion in the casting. The results show that vibration time has significant influence on the fulfilling as well as the internal integrity of the lost foam casting. It was found that the lower vibration time produced comparatively sound casing.

Nonlinear CARS measurement of nitrogen vibrational and rotational temperatures behind hypervelocity strong shock wave

Science.gov (United States)

Osada, Takashi; Endo, Youichi; Kanazawa, Chikara; Ota, Masanori; Maeno, Kazuo

2009-02-01

The hypervelocity strong shock waves are generated, when the space vehicles reenter the atmosphere from space. Behind the shock wave radiative and non-equilibrium flow is generated in front of the surface of the space vehicle. Many studies have been reported to investigate the phenomena for the aerospace exploit and reentry. The research information and data on the high temperature flows have been available to the rational heatproof design of the space vehicles. Recent development of measurement techniques with laser systems and photo-electronics now enables us to investigate the hypervelocity phenomena with greatly advanced accuracy. In this research strong shock waves are generated in low-density gas to simulate the reentry range gas flow with a free-piston double-diaphragm shock tube, and CARS (Coherent Anti-stokes Raman Spectroscopy) measurement method is applied to the hypervelocity flows behind the shock waves, where spectral signals of high space/time resolution are acquired. The CARS system consists of YAG and dye lasers, a spectroscope, and a CCD camera system. We obtain the CARS signal spectrum data by this special time-resolving experiment, and the vibrational and rotational temperatures of N2 are determined by fitting between the experimental spectroscopic profile data and theoretically estimated spectroscopic data.

Nonlinear CARS measurement of nitrogen vibrational and rotational temperatures behind hypervelocity strong shock wave

Energy Technology Data Exchange (ETDEWEB)

Osada, Takashi; Endo, Youichi [Graduate Student, Chiba University 1-33 Yayoi, Inage, Chiba, 263-8522 (Japan); Kanazawa, Chikara [Undergraduate, Chiba University 1-33 Yayoi, Inage, Chiba, 63-8522 (Japan); Ota, Masanori; Maeno, Kazuo, E-mail: maeno@faculty.chiba-u.j [Graduate School of Engineering, Chiba University 1-33 Yayoi, Inage, Chiba, 263-8522 (Japan)

2009-02-01

The hypervelocity strong shock waves are generated, when the space vehicles reenter the atmosphere from space. Behind the shock wave radiative and non-equilibrium flow is generated in front of the surface of the space vehicle. Many studies have been reported to investigate the phenomena for the aerospace exploit and reentry. The research information and data on the high temperature flows have been available to the rational heatproof design of the space vehicles. Recent development of measurement techniques with laser systems and photo-electronics now enables us to investigate the hypervelocity phenomena with greatly advanced accuracy. In this research strong shock waves are generated in low-density gas to simulate the reentry range gas flow with a free-piston double-diaphragm shock tube, and CARS (Coherent Anti-stokes Raman Spectroscopy) measurement method is applied to the hypervelocity flows behind the shock waves, where spectral signals of high space/time resolution are acquired. The CARS system consists of YAG and dye lasers, a spectroscope, and a CCD camera system. We obtain the CARS signal spectrum data by this special time-resolving experiment, and the vibrational and rotational temperatures of N{sub 2} are determined by fitting between the experimental spectroscopic profile data and theoretically estimated spectroscopic data.

Nonlinear CARS measurement of nitrogen vibrational and rotational temperatures behind hypervelocity strong shock wave

International Nuclear Information System (INIS)

Osada, Takashi; Endo, Youichi; Kanazawa, Chikara; Ota, Masanori; Maeno, Kazuo

2009-01-01

The hypervelocity strong shock waves are generated, when the space vehicles reenter the atmosphere from space. Behind the shock wave radiative and non-equilibrium flow is generated in front of the surface of the space vehicle. Many studies have been reported to investigate the phenomena for the aerospace exploit and reentry. The research information and data on the high temperature flows have been available to the rational heatproof design of the space vehicles. Recent development of measurement techniques with laser systems and photo-electronics now enables us to investigate the hypervelocity phenomena with greatly advanced accuracy. In this research strong shock waves are generated in low-density gas to simulate the reentry range gas flow with a free-piston double-diaphragm shock tube, and CARS (Coherent Anti-stokes Raman Spectroscopy) measurement method is applied to the hypervelocity flows behind the shock waves, where spectral signals of high space/time resolution are acquired. The CARS system consists of YAG and dye lasers, a spectroscope, and a CCD camera system. We obtain the CARS signal spectrum data by this special time-resolving experiment, and the vibrational and rotational temperatures of N 2 are determined by fitting between the experimental spectroscopic profile data and theoretically estimated spectroscopic data.

Structural and vibrational spectroscopic studies on charge transfer and ionic hydrogen bonding interactions of melaminium benzoate dihydrate

Science.gov (United States)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Gunasekaran, S.; Rajakumar, P. R.; Anbalagan, G.

2015-06-01

Single crystals of melaminium benzoate dihydrate (MBDH) have been grown from aqueous solution by the slow solvent evaporation method at room temperature. Crystalline nature of the grown crystal has been confirmed by X-ray powder diffraction studies. The optimized geometry, frequency and intensity of the vibrational bands of MBDH were obtained by the Hartree-Fock and density functional theory using B3LYP/cam-B3LYP with 6-311++G(d,p) basis set. The harmonic vibrational frequencies were calculated and the scaled values have been compared with the experimental FT-IR and FT-Raman spectral values. The obtained vibrational wavenumbers and optimized geometric parameters are found to be in good agreement with the experimental data. UV-Visible spectrum was recorded in the region 200-400 nm and the electronic properties, HOMO-LUMO energies and other related electronic parameters are calculated. The isotropic chemical shifts computed by 1H and 13C NMR analysis also show good agreement with experimental observation. Natural bond orbital (NBO) analysis has been performed on MBDH compound to analyze the stability of the molecule arising from hyperconjugative interactions and charge delocalization. Molecular electrostatic potential surface (MEP) has also been performed by DFT/cam-B3LYP method with 6-311++G(d,p) basis set. Differential scanning calorimetric measurements performed on the powder sample indicate the phase transition point approximately at 368 and 358 K for heating and cooling, respectively.

DFT calculations on spectroscopic and structural properties of a NLO chromophore

Science.gov (United States)

Altürk, Sümeyye; Avci, Davut; Tamer, Ömer; Atalay, Yusuf

2016-03-01

The molecular geometry optimization, vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of 2-(1'-(4'''-Methoxyphenyl)-5'-(thien-2″-yl)pyrrol-2'-yl)-1,3-benzothiazole as potential nonlinear optical (NLO) material were calculated using density functional theory (DFT) HSEh1PBE method with 6-311G(d,p) basis set. The best of our knowledge, this study have not been reported to date. Additionally, a detailed vibrational study was performed on the basis of potential energy distribution (PED) using VEDA program. It is noteworthy that NMR chemical shifts are quite useful for understanding the relationship between the molecular structure and electronic properties of molecules. The computed IR and NMR spectra were used to determine the types of the experimental bands observed. Predicted values of structural and spectroscopic parameters of the chromophore were compared with each other so as to display the effects of the different substituents on the spectroscopic and structural properties. Obtained data showed that there is an agreement between the predicted and experimental data.

Vibration of a rotating shaft on hydrodynamic bearings: multi-scales surface effects

International Nuclear Information System (INIS)

Rebufa, Jocelyn

2016-01-01

The hydrodynamic bearing provides good damping properties in rotating machineries. However, the performances of rotor-bearings systems are highly impacted by nonlinear effects that are difficult to analyze. The rotor dynamics prediction requires advanced models for the flow in the bearings. The surface of the bearings seems to have a strong impact on the lubricant flow, acting on the static and dynamic properties of the rotating parts. This study aims to enhance the simulation of the bearings' surface state effect on the motion of the rotating shaft. The flexible shaft interacts with textured hydrodynamic bearings. Multi-scales homogenization is used in a multi-physics algorithm in order to describe the fluid-structure interaction. Different models are used to account for the cavitation phenomenon in the bearings. Nonlinear harmonic methods allow efficient parametric studies of periodic solutions as well as their stability. Moreover, a test rig has been designed to compare predictions to real measurements. Several textured shaft samples modified with femto-seconds LASER surface texturing are tested. In most cases the experimental study showed similar results than the simulation. Enhancements of the vibration behaviors of the rotor-bearing system have been revealed for certain texturing patterns. The self-excited vibration, also known as 'oil whirl' phenomenon, is stabilized on a wide rotating frequency range. However, the simulation tool does not predict well the enhancements that are observed. Vortices in surface texturing patterns have been revealed numerically with Navier-Stokes equation resolution. These results are opposed to the classical lubrication hypothesis. It is also a possible explanation of the enhancements that are experimentally measured with textured bearings. (author) [fr

Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

Science.gov (United States)

Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

2003-10-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Application of comparative vibrational spectroscopic and mechanistic studies in analysis of fisetin structure.

Science.gov (United States)

Dimitrić Marković, Jasmina M; Marković, Zoran S; Milenković, Dejan; Jeremić, Svetlana

2011-12-01

This paper addresses experimental and theoretical research in fisetin (2-(3,4-dihydroxyphenyl)-3,7-dihydroxychromen-4-one) structure by means of experimental IR and Raman spectroscopies and mechanistic calculations. Density Functional Theory calculations, with M05-2X functional and the 6-311+G (2df, p) basis set implemented in the Gaussian 09 package, are performed with the aim to support molecular structure, vibrational bands' positions and their intensities. Potential energy distribution (PED) values and the description of the largest vibrational contributions to the normal modes are calculated. The most intense bands appear in the 1650-1500 cm(-1) wavenumber region. This region involves a combination of the CO, C2C3 and C-C stretching vibrational modes. Most of the bands in the 1500-1000 cm(-1) range involve C-C stretching, O-C stretching and in-plane C-C-H, C-O-H, C-C-O and C-C-C bending vibrations of the rings. The region below 1000 cm(-1) is characteristic to the combination of in plane C-C-C-H, H-C-C-H, C-C-C-C, C-C-O-C and out of plane O-C-C-C, C-C-O-C, C-C-C-C torsional modes. The Raman spectra of baicalein and quercetin were used for qualitative comparison with fisetin spectrum and verification of band assignments. The applied detailed vibrational spectral analysis and the assignments of the bands, proposed on the basis of fundamentals, reproduced the experimental results with high degree of accuracy. Copyright © 2011 Elsevier B.V. All rights reserved.

STUDY OF STATIC ELECTRICITY CHARGE ACCUMULATION ON SURFACE OF FLUOROPOLYMER-4 PRODUCTS USING VIBRATING CAPACITOR METHOD

Directory of Open Access Journals (Sweden)

H. А. Vershina

2012-01-01

Full Text Available The paper presents investigations of processes pertaining to surface charge accumulation and running of fluoropolymer-4 products using vibrating capacitor method. Modification of a measurement technique allowing to register distribution of dielectric surface potential without disturbance of the surface charged state has been described in the paper. The paper contains graphics of spatial distribution of surface potential of fluoropolymer-4 products after various treatments. The paper reveals that thermal treatment (tempering reduces static characteristics of fluoropolymer-4.

Theoretical study of H2/+/ spectroscopic properties. II, III. [2p and 3d excited electronic states

Science.gov (United States)

Beckel, C. L.; Shafi, M.; Peek, J. M.

1973-01-01

Description of the theoretical spectroscopic properties of the 2p pi/sub u/ and 3d sigma/sub g/ excited states of the H2/+/ hydrogen molecular ion. Numerical integration of the Schrodinger equation is used to determine vibration-rotation eigenvalues. Dunham power series expansions are used to determine the equilibrium separation, potential coefficients, and spectroscopic constants. The eigenvalues are used to determine delta-G, Bv, Dv, and Hv.

Experimental and theoretical studies on the structural, spectroscopic and hydrogen bonding on 4-nitro-n-(2,4-dinitrophenyl) benzenamine

Science.gov (United States)

Subhapriya, G.; Kalyanaraman, S.; Jeyachandran, M.; Ragavendran, V.; Krishnakumar, V.

2018-04-01

Synthesized 4-nitro-N-(2,4-dinitrophenyl) benzenamine (NDPBA) molecule was confirmed applying the tool of NMR. Theoretical prediction addressed the NMR chemical shifts and correlated well with the experimental data. The molecule subjected to theoretical DFT at 6-311++G** level unraveled the spectroscopic and structural properties of the NDPBA molecule. Moreover the structural features proved the occurrence of intramolecular Nsbnd H· · O hydrogen bonding in the molecule which was further confirmed with the help of Frontier molecular orbital analysis. Vibrational spectroscopic characterization through FT-IR and Raman experimentally and theoretically gave an account for the vibrational properties. An illustration of the topology of the molecule theoretically helped also in finding the hydrogen bonding energy.

Vibration-rotation spectrum of BH X1Σ+ by Fourier transform emission spectroscopy

Science.gov (United States)

Pianalto, F. S.; O'Brien, L. C.; Keller, P. C.; Bernath, P. F.

1988-06-01

The vibration-rotation emission spectrum of the BH X1Σ+ state was observed with the McMath Fourier transform spectrometer at Kitt Peak. The 1-0, 2-1, and 3-2 bands were observed in a microwave discharge of B2H6 in He. Spectroscopic constants of the individual vibrational levels and equilibrium molecular constants were determined. An RKR potential curve was calculated from the equilibrium constants. Alfred P. Sloan Fellow; Camille and Henry Dreyfus Teacher-Scholar.

Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

Energy Technology Data Exchange (ETDEWEB)

Sanchez-Arenillas, M.; Mateo-Marti, E., E-mail: mateome@cab.inta-csic.es

2015-09-08

Highlights: • Successful adsorption of cystine on pyrite surface under several conditions. • Detailed XPS spectroscopic characterization of cystine adsorption on pyrite surface. • Spectroscopy evidence, oxidation and anoxic conditions adjust molecular adsorption. • Molecular chemistry on pyrite is driven depending on the surrounding conditions. • The cystine/pyrite(100) model is in good agreement with Wächtershäuser’s theory. - Abstract: We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions.

Spectroscopic study of cystine adsorption on pyrite surface: From vacuum to solution conditions

International Nuclear Information System (INIS)

Sanchez-Arenillas, M.; Mateo-Marti, E.

2015-01-01

Highlights: • Successful adsorption of cystine on pyrite surface under several conditions. • Detailed XPS spectroscopic characterization of cystine adsorption on pyrite surface. • Spectroscopy evidence, oxidation and anoxic conditions adjust molecular adsorption. • Molecular chemistry on pyrite is driven depending on the surrounding conditions. • The cystine/pyrite(100) model is in good agreement with Wächtershäuser’s theory. - Abstract: We characterized the adsorption of cystine molecules on pyrite surface via X-ray photoelectron spectroscopy. Anoxic conditions were simulated under ultra-high-vacuum conditions. In contrast, to simulate oxidation conditions, the molecules were adsorbed on pyrite surface from solution. A novel comparative analysis revealed remarkable differences with respect to molecular adsorption and surface chemistry induced by environmental conditions. Molecular adsorption under anoxic conditions was observed to be more favorable, concentrating a large number of molecules on the surface and two different chemical species. In contrast, the presence of oxygen induced an autocatalytic oxidation process on the pyrite surface, which facilitated water binding on pyrite surface and partially blocked molecular adsorption. Pyrite is a highly reactive surface and contains two crucial types of surface functional groups that drive molecular chemistry on the surface depending on the surrounding conditions. Therefore, the system explored in this study holds interesting implications for supporting catalyzed prebiotic chemistry reactions

Fourier transform infrared spectroscopic study of gamma irradiated SiO2 nanoparticles

Science.gov (United States)

Huseynov, Elchin; Garibov, Adil; Mehdiyeva, Ravan; Huseynova, Efsane

2018-03-01

In the present work, nano SiO2 particles are investigated before and after gamma irradiation (25, 50, 75, 100 and 200 kGy) using Fourier transform infrared (FTIR) spectroscopy method for the wavenumber between 400-4000 cm-1. It is found that as a result of spectroscopic analysis, five new peaks have appeared after gamma radiation. Two of new obtained peaks (which are located at 687 cm-1 and 2357 cm-1 of wavenumber) were formed as a result of gamma radiation interaction with Si-O bonds. Another three new peaks (peaks appropriate to 941, 2052 and 2357 cm-1 values of wavenumber) appear as a result of interaction of water with nano SiO2 particles after gamma irradiation. It has been defined as asymmetrical bending vibration, symmetrical bending vibration, symmetrical stretching vibration and asymmetrical stretching vibration of Si-O bonds appropriate to peaks.

Vibrational Spectroscopy as a Promising Toolbox for Analyzing Functionalized Ceramic Membranes.

Science.gov (United States)

Kiefer, Johannes; Bartels, Julia; Kroll, Stephen; Rezwan, Kurosch

2018-01-01

Ceramic materials find use in many fields including the life sciences and environmental engineering. For example, ceramic membranes have shown to be promising filters for water treatment and virus retention. The analysis of such materials, however, remains challenging. In the present study, the potential of three vibrational spectroscopic methods for characterizing functionalized ceramic membranes for water treatment is evaluated. For this purpose, Raman scattering, infrared (IR) absorption, and solvent infrared spectroscopy (SIRS) were employed. The data were analyzed with respect to spectral changes as well as using principal component analysis (PCA). The Raman spectra allow an unambiguous discrimination of the sample types. The IR spectra do not change systematically with functionalization state of the material. Solvent infrared spectroscopy allows a systematic distinction and enables studying the molecular interactions between the membrane surface and the solvent.

Translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I

Science.gov (United States)

Takahashi, Masae; Ishikawa, Yoichi

2013-06-01

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.

Mode pattern of internal flow in a water droplet on a vibrating hydrophobic surface.

Science.gov (United States)

Kim, Hun; Lim, Hee-Chang

2015-06-04

The objective of this study is to understand the mode pattern of the internal flow in a water droplet placed on a hydrophobic surface that periodically and vertically vibrates. As a result, a water droplet on a vibrating hydrophobic surface has a typical shape that depends on each resonance mode, and, additionally, we observed a diversified lobe size and internal flows in the water droplet. The size of each lobe at the resonance frequency was relatively greater than that at the neighboring frequencies, and the internal flow of the nth order mode was also observed in the flow visualization. In general, large symmetrical flow streams were generated along the vertical axis in each mode, with a large circulating movement from the bottom to the top, and then to the triple contact line along the droplet surface. In contrast, modes 2 and 4 generated a Y-shaped flow pattern, in which the flow moved to the node point in the lower part of the droplet, but modes 6 and 8 had similar patterns, with only a little difference. In addition, as a result of the PIV measurement, while the flow velocity of mode 4 was faster than that of model 2, those of modes 6 and 8 were almost similar.

Experimental and theoretical studies on the vibrational structure on disperse vanadium and titanium oxide; Experimentelle und theoretische Untersuchungen zur Schwingungsstruktur an dispersem Vanadium- und Titanoxid

Energy Technology Data Exchange (ETDEWEB)

Nitsche, David

2014-10-20

identified as a V=O stretch vibrations, where the difference is caused by the phase shift between the anchoring V-O-Si vibration. By combining results from spectroscopy and simulations the surface structure of vanadia and titania species could described in detail. Under highly dispersed conditions the surface structure can not be completely described by an isolated, trigrafted species as has been traditionally proposed in the literature. Instead, the vanadia and titania surface species can oligomerize even under highly dispersed conditions. The present study shows that the assignment of Raman bands is much more complex than previously assumed. Based on a pure spectroscopic or theoretical study an unambiguous assignment of the Raman bands ist not possible. However, by combining theoretical and spectroscopic approaches, the present study succeeded in developing a more detailed picture of the surface species under hydrated and dehydrated conditions and deepening the understanding of the vibrational structure of silica supported vanadia and titania surface species.

Electric field dependent structural and vibrational properties of the Si(100)-H(2 x 1) surface and its implications for STM induced hydrogen desorption

DEFF Research Database (Denmark)

Stokbro, Kurt

1999-01-01

We report a first principles study of the structure and the vibrational properties of the Si(100)-H(2 x 1) surface in an electric field. The calculated vibrational parameters are used to model the vibrational modes in the presence of the electric field corresponding to a realistic scanning...

Surface quality monitoring for process control by on-line vibration analysis using an adaptive spline wavelet algorithm

Science.gov (United States)

Luo, G. Y.; Osypiw, D.; Irle, M.

2003-05-01

The dynamic behaviour of wood machining processes affects the surface finish quality of machined workpieces. In order to meet the requirements of increased production efficiency and improved product quality, surface quality information is needed for enhanced process control. However, current methods using high price devices or sophisticated designs, may not be suitable for industrial real-time application. This paper presents a novel approach of surface quality evaluation by on-line vibration analysis using an adaptive spline wavelet algorithm, which is based on the excellent time-frequency localization of B-spline wavelets. A series of experiments have been performed to extract the feature, which is the correlation between the relevant frequency band(s) of vibration with the change of the amplitude and the surface quality. The graphs of the experimental results demonstrate that the change of the amplitude in the selective frequency bands with variable resolution (linear and non-linear) reflects the quality of surface finish, and the root sum square of wavelet power spectrum is a good indication of surface quality. Thus, surface quality can be estimated and quantified at an average level in real time. The results can be used to regulate and optimize the machine's feed speed, maintaining a constant spindle motor speed during cutting. This will lead to higher level control and machining rates while keeping dimensional integrity and surface finish within specification.

Spectroscopic Characterization of Omeprazole and Its Salts

Directory of Open Access Journals (Sweden)

Tomislav Vrbanec

2017-01-01

Full Text Available During drug development, it is important to have a suitable crystalline form of the active pharmaceutical ingredient (API. Mostly, the basic options originate in the form of free base, acid, or salt. Substances that are stable only within a certain pH range are a challenge for the formulation. For the prazoles, which are known to be sensitive to degradation in an acid environment, the formulation is stabilized with alkaline additives or with the application of API formulated as basic salts. Therefore, preparation and characterization of basic salts are needed to monitor any possible salinization of free molecules. We synthesized salts of omeprazole from the group of alkali metals (Li, Na, and K and alkaline earth metals (Mg, Ca. The purpose of the presented work is to demonstrate the applicability of vibrational spectroscopy to discriminate between the OMP and OMP-salt molecules. For this reason, the physicochemical properties of 5 salts were probed using infrared and Raman spectroscopy, NMR, TG, DSC, and theoretical calculation of vibrational frequencies. We found out that vibrational spectroscopy serves as an applicable spectroscopic tool which enables an accurate, quick, and nondestructive way to determine the characteristic of OMP and its salts.

A new potential energy surface for vibration-vibration coupling in HF-HF collisions. Formulation and quantal scattering calculations

Science.gov (United States)

Schwenke, David W.; Truhlar, Donald G.

1988-04-01

We present new ab initio calculations of the HF-HF interaction potential for the case where both molecules are simultaneously displaced from their equilibrium internuclear distance. These and previous ab initio calculations are then fit to a new analytic representation which is designed to be efficient to evaluate and to provide an especially faithful account of the forces along the vibrational coordinates. We use the new potential for two sets of quantal scattering calculations for collisions in three dimensions with total angular momentum zero. First we test that the angular harmonic representation of the anisotropy is adequate by comparing quantal rigid rotator calculations to those carried out for potentials involving higher angular harmonics and for which the expansion in angular harmonics is systematically increased to convergence. Then we carry out large-scale quantal calculations of vibration-vibration energy transfer including the coupling of both sets of vibrational and rotational coordinates. These calculations indicate that significant rotational energy transfer accompanies the vibration-to-vibration energy transfer process.

Three-body interactions in liquid and solid hydrogen: Evidence from vibrational spectroscopy

Science.gov (United States)

Hinde, Robert

2008-03-01

In the cryogenic low-density liquid and solid phases of H2 and D2, the H2 and D2 molecules retain good rotational and vibrational quantum numbers that characterize their internal degrees of freedom. High-resolution infrared and Raman spectroscopic experiments provide extremely sensitive probes of these degrees of freedom. We present here fully-first-principles calculations of the infrared and Raman spectra of liquid and solid H2 and D2, calculations that employ a high-quality six-dimensional coupled-cluster H2-H2 potential energy surface and quantum Monte Carlo treatments of the single-molecule translational degrees of freedom. The computed spectra agree very well with experimental results once we include three-body interactions among the molecules, interactions which we also compute using coupled-cluster quantum chemical methods. We predict the vibrational spectra of liquid and solid H2 at several temperatures and densities to provide a framework for interpreting recent experiments designed to search for superfluid behavior in small H2 droplets. We also present preliminary calculations of the spectra of mixed H2/D2 solids that show how positional disorder affects the spectral line shapes in these systems.

Vibrational spectroscopic, structural and nonlinear optical activity studies on 2-amino-3-chloro-5-trifluoromethyl pyridine: A DFT approach

Science.gov (United States)

Asath, R. Mohamed; Premkumar, S.; Rekha, T. N.; Jawahar, A.; Mathavan, T.; Benial, A. Milton Franklin

2016-05-01

The conformational analysis was carried out for 2-amino-3-chloro-5-trifluoromethylpyridine using potential energy surface (PES) scan and the most stable optimized conformer was predicted. The theoretical vibrational frequencies were calculated for the optimized geometry using DFT/B3LYP cc-pVQZ basis set by Gaussian 09 Program. The vibrational frequencies were assigned on the basis of potential energy distribution calculation using VEDA 4.0 program package. The Mulliken atomic charge values were calculated. In the Frontier molecular orbitals analysis, the molecular reactivity, kinetic stability, intermolecular charge transfer studies and the calculation of ionization energy, electron affinity, global hardness, chemical potential, electrophilicity index and softness of the molecule were carried out. The nonlinear optical (NLO) activity was studied and the first order hyperpolarizability value was computed, which was 3.48 times greater than the urea. The natural bond orbital analysis was also performed to confirm the NLO activity of the molecule. Hence, the ACTP molecule is a promising candidate for NLO materials.

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

Science.gov (United States)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

Vibrational properties of the Au-(√{3 }×√{3 } )/Si(111) surface reconstruction

Science.gov (United States)

Halbig, B.; Liebhaber, M.; Bass, U.; Geurts, J.; Speiser, E.; Räthel, J.; Chandola, S.; Esser, N.; Krenz, M.; Neufeld, S.; Schmidt, W. G.; Sanna, S.

2018-01-01

The vibrational properties of the Au-induced (√{3 }×√{3 })R 30∘ reconstruction of the Si(111) surface are investigated by polarized surface Raman spectroscopy and density-functional theory. The Raman measurements are performed in situ at room temperature as well as 20 K, and they reveal the presence of vibrational eigenmodes in the spectral range from 20 to 450 cm-1. In particular, two peaks of E symmetry at 75 and 183 cm-1 dominate the spectra. No substantial difference between room- and low-temperature spectra is observed, suggesting that the system does not undergo a phase transition down to 20 K. First-principles calculations are performed based on the structural models discussed in the literature. The thermodynamically stable conjugate honeycomb-chained-trimer model (CHCT) [Surf. Sci. 275, L691 (1992), 10.1016/0039-6028(92)90785-5] leads to phonon eigenvalues compatible with the experimental observations in the investigated spectral range. On the basis of the phonon eigenfrequencies, symmetries, and Raman intensities, we assign the measured spectral features to the calculated phonon modes. The good agreement between measured and calculated modes provides a strong argument in favor of the CHCT model.

Process optimization for ultrasonic vibration assisted polishing of micro-structured surfaces on super hard material

Science.gov (United States)

Sun, Zhiyuan; Guo, Bing; Rao, Zhimin; Zhao, Qingliang

2014-08-01

In consideration of the excellent property of SiC, the ground micro-structured surface quality is hard to meet the requirement - consequently the ultrasonic vibration assisted polishing (UVAP) of micro-structures of molds is proposed in this paper. Through the orthogonal experiment, the parameters of UVAP of micro-structures were optimized. The experimental results show that, abrasive polishing process, the effect of the workpiece feed rate on the surface roughness (Ra), groove tip radius (R) and material removal rate (MRR) of micro-structures is significant. While, the UVAP, the most significant effect factor for Ra, R and MRR is the ultrasonic amplitude of the ultrasonic vibration. In addition, within the scope of the polishing process parameters selected by preliminary experiments, ultrasonic amplitude of 2.5μm, polishing force of 0.5N, workpiece feed rate of 5 mm·min-1, polishing wheel rotational speed of 50rpm, polishing time of 35min, abrasive size of 100nm and the polishing liquid concentration of 15% is the best technology of UVAP of micro-structures. Under the optimal parameters, the ground traces on the micro-structured surface were removed efficiently and the integrity of the edges of the micro-structure after grinding was maintained efficiently.

Theoretical and experimental study of the vibrational excitations in ethane monolayers adsorbed on graphite (0001) surfaces

DEFF Research Database (Denmark)

Hansen, Flemming Yssing; Taub, H.

1987-01-01

The collective vibrational excitations of two different crystalline monolayer phases of ethane (C2H6) adsorbed on the graphite (0001) surface have been investigated theoretically and experimentally. The monolayer phases studied are the commensurate 7/8 ×4 structure in which the ethane molecules lie...

Accurate spectroscopic characterization of protonated oxirane: a potential prebiotic species in Titan's atmosphere

International Nuclear Information System (INIS)

Giacomo Ciamician, Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy))" data-affiliation=" (Dipartimento di Chimica Giacomo Ciamician, Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy))" >Puzzarini, Cristina; Ali, Ashraf; Biczysko, Malgorzata; Barone, Vincenzo

2014-01-01

An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm –1 for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan's atmosphere but also in the interstellar medium.

Accurate spectroscopic characterization of protonated oxirane: a potential prebiotic species in Titan's atmosphere

Energy Technology Data Exchange (ETDEWEB)

Puzzarini, Cristina [Dipartimento di Chimica " Giacomo Ciamician," Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy); Ali, Ashraf [NASA Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Biczysko, Malgorzata; Barone, Vincenzo, E-mail: cristina.puzzarini@unibo.it [Scuola Normale Superiore, Piazza dei Cavalieri 7, I-56126 Pisa (Italy)

2014-09-10

An accurate spectroscopic characterization of protonated oxirane has been carried out by means of state-of-the-art computational methods and approaches. The calculated spectroscopic parameters from our recent computational investigation of oxirane together with the corresponding experimental data available were used to assess the accuracy of our predicted rotational and IR spectra of protonated oxirane. We found an accuracy of about 10 cm{sup –1} for vibrational transitions (fundamentals as well as overtones and combination bands) and, in relative terms, of 0.1% for rotational transitions. We are therefore confident that the spectroscopic data provided herein are a valuable support for the detection of protonated oxirane not only in Titan's atmosphere but also in the interstellar medium.

Full-Dimensional Quantum Calculations of Vibrational Levels of NH4(+) and Isotopomers on An Accurate Ab Initio Potential Energy Surface.

Science.gov (United States)

Yu, Hua-Gen; Han, Huixian; Guo, Hua

2016-04-14

Vibrational energy levels of the ammonium cation (NH4(+)) and its deuterated isotopomers are calculated using a numerically exact kinetic energy operator on a recently developed nine-dimensional permutation invariant semiglobal potential energy surface fitted to a large number of high-level ab initio points. Like CH4, the vibrational levels of NH4(+) and ND4(+) exhibit a polyad structure, characterized by a collective quantum number P = 2(v1 + v3) + v2 + v4. The low-lying vibrational levels of all isotopomers are assigned and the agreement with available experimental data is better than 1 cm(-1).

Vibrational Spectroscopy of Chromatographic Interfaces

Energy Technology Data Exchange (ETDEWEB)

Jeanne E. Pemberton

2011-03-10

Chromatographic separations play a central role in DOE-supported fundamental research related to energy, biological systems, the environment, and nuclear science. The overall portfolio of research activities in the Separations and Analysis Program within the DOE Office of Basic Energy Sciences includes support for activities designed to develop a molecular-level understanding of the chemical processes that underlie separations for both large-scale and analytical-scale purposes. The research effort funded by this grant award was a continuation of DOE-supported research to develop vibrational spectroscopic methods to characterize the interfacial details of separations processes at a molecular level.

Vibrational spectroscopy in diagnosis and screening

CERN Document Server

Severcan, F

2012-01-01

In recent years there has been a tremendous growth in the use of vibrational spectroscopic methods for diagnosis and screening. These applications range from diagnosis of disease states in humans, such as cancer, to rapid identification and screening of microorganisms. The growth in such types of studies has been possible thanks to advances in instrumentation and associated computational and mathematical tools for data processing and analysis. This volume of Advances in Biomedical Spectroscopy contains chapters from leading experts who discuss the latest advances in the application of Fourier

Study on Effect of Ultrasonic Vibration on Grinding Force and Surface Quality in Ultrasonic Assisted Micro End Grinding of Silica Glass

Directory of Open Access Journals (Sweden)

Zhang Jianhua

2014-01-01

Full Text Available Ultrasonic vibration assisted micro end grinding (UAMEG is a promising processing method for micro parts made of hard and brittle materials. First, the influence of ultrasonic assistance on the mechanism of this processing technology is theoretically analyzed. Then, in order to reveal the effects of ultrasonic vibration and grinding parameters on grinding forces and surface quality, contrast grinding tests of silica glass with and without ultrasonic assistance using micro radial electroplated diamond wheel are conducted. The grinding forces are measured using a three-component dynamometer. The surface characteristics are detected using the scanning electron microscope. The experiment results demonstrate that grinding forces are significantly reduced by introducing ultrasonic vibration into conventional micro end grinding (CMEG of silica glass; ultrasonic assistance causes inhibiting effect on variation percentages of tangential grinding force with grinding parameters; ductile machining is easier to be achieved and surface quality is obviously improved due to ultrasonic assistance in UAMEG. Therefore, larger grinding depth and feed rate adopted in UAMEG can lead to the improvement of removal rate and machining efficiency compared with CMEG.

Analysis of structure and vibrational dynamics of the BeTe(001) surface using X-ray diffraction, Raman spectroscopy, and density functional theory

DEFF Research Database (Denmark)

Kumpf, C.; Müller, A.; Weigand, W.

2003-01-01

The atomic structure and lattice dynamics of epitaxial BeTe(001) thin films are derived from surface x-ray diffraction and Raman spectroscopy. On the Te-rich BeTe(001) surface [1 (1) over bar0]-oriented Te dimers are identified. They cause a (2 X 1) superstructure and induce a pronounced buckling...... in the underlying Te layer. The Be-rich surface exhibits a (4 X 1) periodicity with alternating Te dimers and Te-Be-Te trimers. A vibration eigenfrequency of 165 cm(-1) is observed for the Te-rich surface, while eigenmodes at 157 and 188 cm(-1) are found for the Be-rich surface. The experimentally derived atomic...... geometry and the vibration modes are in very good agreement with the results of density functional theory calculations....

Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

Science.gov (United States)

Lopaev, D. V.; Malykhin, E. M.; Zyryanov, S. M.

2011-01-01

Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature TV was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O(3P), O2, O2(1Δg) and O3 molecules in different vibrational states. The agreement of O3 and O(3P) density profiles and TV calculated in the model with observed ones was reached by varying the single model parameter—ozone production probability (\\gamma_{O_{3}}) on the quartz tube surface on the assumption that O3 production occurs mainly in the surface recombination of physisorbed O(3P) and O2. The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse \\gamma_{O_{3}} data obtained in the kinetic model. A good agreement between the experimental data and the data of both models—the kinetic 1D model and the phenomenological surface model—was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up the

Surface recombination of oxygen atoms in O2 plasma at increased pressure: II. Vibrational temperature and surface production of ozone

International Nuclear Information System (INIS)

Lopaev, D V; Malykhin, E M; Zyryanov, S M

2011-01-01

Ozone production in an oxygen glow discharge in a quartz tube was studied in the pressure range of 10-50 Torr. The O 3 density distribution along the tube diameter was measured by UV absorption spectroscopy, and ozone vibrational temperature T V was found comparing the calculated ab initio absorption spectra with the experimental ones. It has been shown that the O 3 production mainly occurs on a tube surface whereas ozone is lost in the tube centre where in contrast the electron and oxygen atom densities are maximal. Two models were used to analyse the obtained results. The first one is a kinetic 1D model for the processes occurring near the tube walls with the participation of the main particles: O( 3 P), O 2 , O 2 ( 1 Δ g ) and O 3 molecules in different vibrational states. The agreement of O 3 and O( 3 P) density profiles and T V calculated in the model with observed ones was reached by varying the single model parameter-ozone production probability (γ O 3 ) on the quartz tube surface on the assumption that O 3 production occurs mainly in the surface recombination of physisorbed O( 3 P) and O 2 . The phenomenological model of the surface processes with the participation of oxygen atoms and molecules including singlet oxygen molecules was also considered to analyse γ O 3 data obtained in the kinetic model. A good agreement between the experimental data and the data of both models-the kinetic 1D model and the phenomenological surface model-was obtained in the full range of the studied conditions that allowed consideration of the ozone surface production mechanism in more detail. The important role of singlet oxygen in ozone surface production was shown. The O 3 surface production rate directly depends on the density of physisorbed oxygen atoms and molecules and can be high with increasing pressure and energy inputted into plasma while simultaneously keeping the surface temperature low enough. Using the special discharge cell design, such an approach opens up

ATR-FTIR and density functional theory study of the structures, energetics, and vibrational spectra of phosphate adsorbed onto goethite.

Science.gov (United States)

Kubicki, James D; Paul, Kristian W; Kabalan, Lara; Zhu, Qing; Mrozik, Michael K; Aryanpour, Masoud; Pierre-Louis, Andro-Marc; Strongin, Daniel R

2012-10-16

Periodic plane-wave density functional theory (DFT) and molecular cluster hybrid molecular orbital-DFT (MO-DFT) calculations were performed on models of phosphate surface complexes on the (100), (010), (001), (101), and (210) surfaces of α-FeOOH (goethite). Binding energies of monodentate and bidentate HPO(4)(2-) surface complexes were compared to H(2)PO(4)(-) outer-sphere complexes. Both the average potential energies from DFT molecular dynamics (DFT-MD) simulations and energy minimizations were used to estimate adsorption energies for each configuration. Molecular clusters were extracted from the energy-minimized structures of the periodic systems and subjected to energy reminimization and frequency analysis with MO-DFT. The modeled P-O and P---Fe distances were consistent with EXAFS data for the arsenate oxyanion that is an analog of phosphate, and the interatomic distances predicted by the clusters were similar to those of the periodic models. Calculated vibrational frequencies from these clusters were then correlated with observed infrared bands. Configurations that resulted in favorable adsorption energies were also found to produce theoretical vibrational frequencies that correlated well with experiment. The relative stability of monodentate versus bidentate configurations was a function of the goethite surface under consideration. Overall, our results show that phosphate adsorption onto goethite occurs as a variety of surface complexes depending on the habit of the mineral (i.e., surfaces present) and solution pH. Previous IR spectroscopic studies may have been difficult to interpret because the observed spectra averaged the structural properties of three or more configurations on any given sample with multiple surfaces.

Spectroscopic characterization of the ethyl radical-water complex.

Science.gov (United States)

Lin, Chen; Finney, Brian A; Laufer, Allan H; Anglada, Josep M; Francisco, Joseph S

2016-10-14

An ab initio investigation has been employed to determine the structural and spectroscopic parameters, such as rotational constants, vibrational frequencies, vertical excitation energies, and the stability of the ethyl-water complex. The ethyl-water complex has a binding energy of 1.15 kcal⋅mol -1 . The interaction takes place between the hydrogen of water and the unpaired electron of the radical. This interaction is found to produce a red shift in the OH stretching bands of water of ca. 84 cm -1 , and a shift of all UV absorption bands to higher energies.

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Science.gov (United States)

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in

Salt Effects on Surface Structures of Polyelectrolyte Multilayers (PEMs) Investigated by Vibrational Sum Frequency Generation (SFG) Spectroscopy.

Science.gov (United States)

Ge, Aimin; Matsusaki, Michiya; Qiao, Lin; Akashi, Mitsuru; Ye, Shen

2016-04-26

Sum frequency generation (SFG) vibrational spectroscopy was employed to investigate the surface structures of polyelectrolyte multilayers (PEMs) constructed by sequentially alternating adsorption of poly(diallyldimethylammonium chloride) (PDDA) and poly(styrenesulfonate) (PSS). It was found that the surface structures and surface charge density of the as-deposited PEMs of PDDA/PSS significantly depend on the concentration of sodium chloride (NaCl) present in the polyelectrolyte solutions. Furthermore, it was found that the surface structure of the as-deposited PEMs is in a metastable state and will reach the equilibrium state by diffusion of the polyelectrolyte chain after an aging process, resulting in a polyelectrolyte mixture on the PEM surfaces.

Two-dimensional vibrational spectroscopy of the amide I band of crystalline acetanilide: Fermi resonance, conformational substates, or vibrational self-trapping?

Science.gov (United States)

Edler, J.; Hamm, P.

2003-08-01

Two-dimensional infrared (2D-IR) spectroscopy is applied to investigate acetanilide, a molecular crystal consisting of quasi-one-dimensional hydrogen bonded peptide units. The amide-I band exhibits a double peak structure, which has been attributed to different mechanisms including vibrational self-trapping, a Fermi resonance, or the existence of two conformational substates. The 2D-IR spectrum of crystalline acetanilide is compared with that of two different molecular systems: (i) benzoylchloride, which exhibits a strong symmetric Fermi resonance and (ii) N-methylacetamide dissolved in methanol which occurs in two spectroscopically distinguishable conformations. Both 2D-IR spectra differ significantly from that of crystalline acetanilide, proving that these two alternative mechanisms cannot account for the anomalous spectroscopy of crystalline acetanilide. On the other hand, vibrational self-trapping of the amide-I band can naturally explain the 2D-IR response.

Conformational, vibrational spectroscopic and quantum chemical studies on 5-methoxyindole-3-carboxaldehyde: A DFT approach

Science.gov (United States)

Jeyaseelan, S. Christopher; Hussain, Shamima; Premkumar, R.; Rekha, T. N.; Benial, A. Milton Franklin

2018-04-01

Indole and its derivatives are considered as good ligands for various disease causing proteins in human because of presence of the single nitrogen atom. In the present study, the potential energy surface scan was performed for the most stable molecular structure of the 5-Methoxyindole-3-carboxaldehyde (MICA) molecule. The most stable molecular structure was optimized by DFT/B3LYP method with 6-311G++ (d, p) basis set using Gaussian 09 program package. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculations using VEDA 4.0 program. The Frontier molecular orbitals analysis was performed and related molecular propertieswere calculated. The possible electrophilic and nucleophilic reactive sites of the molecule were studied using molecular electrostatic potential analysis, which confirms the bioactivity of the molecule. The natural bond orbital analysis was also performed to confirm the bioactivity of the title molecule.

The influence of the fault zone width on land surface vibrations after the high-energy tremor in the "Rydułtowy-Anna" hard coal mine

Science.gov (United States)

Pilecka, Elżbieta; Szwarkowski, Dariusz

2018-04-01

In the article, a numerical analysis of the impact of the width of the fault zone on land surface tremors on the area of the "Rydułtowy - Anna" hard coal mine was performed. The analysis covered the dynamic impact of the actual seismic wave after the high-energy tremor of 7 June 2013. Vibrations on the land surface are a measure of the mining damage risk. It is particularly the horizontal components of land vibrations that are dangerous to buildings which is reflected in the Mining Scales of Intensity (GSI) of vibrations. The run of a seismic wave in the rock mass from the hypocenter to the area's surface depends on the lithology of the area and the presence of fault zones. The rock mass network cut by faults of various widths influences the amplitude of tremor reaching the area's surface. The analysis of the impact of the width of the fault zone was done for three alternatives.

Spectroscopic and vibrational analysis of the methoxypsoralen system: A comparative experimental and theoretical study

Science.gov (United States)

Liu, Y.; Yuan, H.; Vo-Dinh, T.

2013-03-01

Raman spectra measurements and density functional theory (DFT) calculations were performed to investigate three psoralens: 5-amino-8-methoxypsoralen (5-A-8-MOP), 5-methoxypsoralen (5-MOP) and 8-methoxypsoralen (8-MOP) with the aim of differentiating these similar bioactive molecules. The Raman spectra were recorded in the region 300-3500 cm-1. All three psoralens were found to have similar Raman spectrum in the region 1500-1650 cm-1. 5-A-8-MOP can be easily differentiated from 5-MOP or 8-MOP based on the Raman spectrum. The Raman spectrum differences at 651 and 795 cm-1 can be used to identify 5-MOP from 8-MOP. The theoretically computed vibrational frequencies and relative peak intensities were compared with experimental data. DFT calculations using the B3LYP method and 6-311++G(d,p) basis set were found to yield results that are very comparable to experimental Raman spectra. Detailed vibrational assignments were performed with DFT calculations and the potential energy distribution (PED) obtained from the Vibrational Energy Distribution Analysis (VEDA) program.

Spectroscopic identification of binary and ternary surface complexes of Np(V) on gibbsite.

Science.gov (United States)

Gückel, Katharina; Rossberg, André; Müller, Katharina; Brendler, Vinzenz; Bernhard, Gert; Foerstendorf, Harald

2013-12-17

For the first time, detailed molecular information on the Np(V) sorption species on amorphous Al(OH)3 and crystalline gibbsite was obtained by in situ time-resolved Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The results consistently demonstrate the formation of mononuclear inner sphere complexes of the NpO2(+) ion irrespective of the prevailing atmospheric condition. The impact of the presence of atmospheric equivalent added carbonate on the speciation in solution and on the surfaces becomes evident from vibrational data. While the 1:1 aqueous carbonato species (NpO2CO3(-)) was found to become predominant in the circumneutral pH range, it is most likely that this species is sorbed onto the gibbsite surface as a ternary inner sphere surface complex where the NpO2(+) moiety is directly coordinated to the functional groups of the gibbsite's surface. These findings are corroborated by results obtained from EXAFS spectroscopy providing further evidence for a bidentate coordination of the Np(V) ion on amorphous Al(OH)3. The identification of the Np(V) surface species on gibbsite constitutes a basic finding for a comprehensive description of the dissemination of neptunium in groundwater systems.

Vibrational spectroscopic investigation of p-, m- and o-nitrobenzonitrile by using Hartree-Fock and density functional theory

Science.gov (United States)

Sert, Y.; Ucun, F.

2013-08-01

In the present work, the theoretical vibrational spectra of p-, m- and o-nitrobenzonitrile molecules have been analyzed. The harmonic vibrational frequencies and geometric parameters (bond lengths and bond angles) of these molecules have been calculated using ab initio Hartree-Fock and density functional theory methods with 6-311++G(d,p) basis set by Gaussian 03 W, for the first time. Assignments of the vibrational frequencies have been performed by potential energy distribution by using VEDA 4 program. The optimized geometric parameters and harmonic vibrational frequencies have been compared with the corresponding experimental data and seen to be in a good agreement with each other. Also, the highest occupied molecular orbital and lowest unoccupied molecular orbital energies have been obtained.

Intrinsic chirality and prochirality at Air/R-(+)- and S-(-)-limonene interfaces: spectral signatures with interference chiral sum-frequency generation vibrational spectroscopy.

Science.gov (United States)

Fu, Li; Zhang, Yun; Wei, Zhe-Hao; Wang, Hong-Fei

2014-09-01

We report in this work detailed measurements of the chiral and achiral sum-frequency vibrational spectra in the C-H stretching vibration region (2800-3050 cm(-1)) of the air/liquid interfaces of R-(+)-limonene and S-(-)-limonene, using the recently developed high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS). The achiral SFG spectra of R-limonene and S-limonene, as well as the RS racemic mixture (50/50 equal amount mixture), show that the corresponding molecular groups of the R and S enantiomers are with the same interfacial orientations. The interference chiral SFG spectra of the limonene enantiomers exhibit a spectral signature from the chiral response of the Cα-H stretching mode, and a spectral signature from the prochiral response of the CH(2) asymmetric stretching mode, respectively. The chiral spectral feature of the Cα-H stretching mode changes sign from R-(+)-limonene to S-(-)-limonene surfaces, and disappears for the RS racemic mixture surface. While the prochiral spectral feature of the CH(2) asymmetric stretching mode is the same for R-(+)-limonene and S-(-)-limonene surfaces, and also surprisingly remains the same for the RS racemic mixture surface. Therefore, the structures of the R-(+)-limonene and the S-(-)-limonene at the liquid interfaces are nevertheless not mirror images to each other, even though the corresponding groups have the same tilt angle from the interfacial normal, i.e., the R-(+)-limonene and the S-(-)-limonene at the surface are diastereomeric instead of enantiomeric. These results provide detailed information in understanding the structure and chirality of molecular interfaces and demonstrate the sensitivity and potential of SFG-VS as a unique spectroscopic tool for chirality characterization and chiral recognition at the molecular interface. © 2014 Wiley Periodicals, Inc.

High-Accuracy Quartic Force Field Calculations for the Spectroscopic Constants and Vibrational Frequencies of 1(exp 1)A' l-C3H(-): A Possible Link to Lines Observed in the Horsehead Nebula PDR

Science.gov (United States)

Fortenberry, Ryan C.; Huang, Xinchuan; Crawford, T. Daniel; Lee, Timothy J.

2013-01-01

It has been shown that rotational lines observed in the Horsehead nebula photon-dominated-region (PDR) are probably not caused by l-C3H+, as was originally suggested. In the search for viable alternative candidate carriers, quartic force fields are employed here to provide highly accurate rotational constants, as well as fundamental vibrational frequencies, for another candidate carrier: 1 (sup 1)A' C3H(-). The ab initio computed spectroscopic constants provided in this work are, compared to those necessary to define the observed lines, as accurate as the computed spectroscopic constants for many of the known interstellar anions. Additionally, the computed D-eff for C3H(-) is three times closer to the D deduced from the observed Horsehead nebula lines relative to l-C3H(+). As a result, 1 (sup 1)A' C3H(-). is a more viable candidate for these observed rotational transitions and would be the seventh confirmed interstellar anion detected within the past decade and the first C(sub n)H(-) molecular anion with an odd n.

Effect of surface structure on catalytic reactions: A sum frequency generation surface vibrational spectroscopy study

International Nuclear Information System (INIS)

McCrea, Keith R.

2001-01-01

In the results discussed above, it is clear that Sum Frequency Generation (SFG) is a unique tool that allows the detection of vibrational spectra of adsorbed molecules present on single crystal surfaces under catalytic reaction conditions. Not only is it possible to detect active surface intermediates, it is also possible to detect spectator species which are not responsible for the measured turnover rates. By correlating high-pressure SFG spectra under reaction conditions and gas chromatography (GC) kinetic data, it is possible to determine which species are important under reaction intermediates. Because of the flexibility of this technique for studying surface intermediates, it is possible to determine how the structures of single crystal surfaces affect the observed rates of catalytic reactions. As an example of a structure insensitive reaction, ethylene hydrogenation was explored on both Pt(111) and Pt(100). The rates were determined to be essentially the same. It was observed that both ethylidyne and di-(sigma) bonded ethylene were present on the surface under reaction conditions on both crystals, although in different concentrations. This result shows that these two species are not responsible for the measured turnover rate, as it would be expected that one of the two crystals would be more active than the other, since the concentration of the surface intermediate would be different on the two crystals. The most likely active intermediates are weakly adsorbed molecules such as(pi)-bonded ethylene and ethyl. These species are not easily detected because their concentration lies at the detection limit of SFG. The SFG spectra and GC data essentially show that ethylene hydrogenation is structure insensitive for Pt(111) and Pt(100). SFG has proven to be a unique and excellent technique for studying adsorbed species on single crystal surfaces under high-pressure catalytic reactions. Coupled with kinetic data obtained from gas chromatography measurements, it can

Hydrogen bonds in crystalline d-alanine: diffraction and spectroscopic evidence for differences between enantiomers

Directory of Open Access Journals (Sweden)

Ezequiel A. Belo

2018-01-01

Full Text Available Enantiomeric amino acids have specific physiological functions in complex biological systems. Systematic studies focusing on the solid-state properties of d-amino acids are, however, still limited. To shed light on this field, structural and spectroscopic studies of d-alanine using neutron powder diffraction, polarized Raman scattering and ab initio calculations of harmonic vibrational frequencies were carried out. Clear changes in the number of vibrational modes are observed as a function of temperature, which can be directly connected to variations of the N—D bond lengths. These results reveal dissimilarities in the structural properties of d-alanine compared with l-alanine.

Theoretical spectroscopic investigations of HNS{sup q} and HSN{sup q} (q = 0, +1, −1) in the gas phase

Energy Technology Data Exchange (ETDEWEB)

Ben Yaghlane, S., E-mail: roberto.linguerri@u-pem.fr, E-mail: saidayagh@gmail.com; Jaidane, N.-E. [Laboratoire de Spectroscopie Atomique, Moléculaire et Applications - LSAMA, Université de Tunis El Manar, Tunis (Tunisia); Cotton, C. E.; Francisco, J. S. [Department of Chemistry and Department of Earth and Atmospheric Science, Purdue University, West Lafayette, Indiana 49707 (United States); Al Mogren, M. M. [Chemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451 (Saudi Arabia); Linguerri, R., E-mail: roberto.linguerri@u-pem.fr, E-mail: saidayagh@gmail.com; Hochlaf, M. [Laboratoire Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 bd Descartes, 77454 Marne-la-Vallée (France)

2014-06-28

We performed accurate ab initio investigations of the geometric parameters and the vibrational structure of neutral HNS/HSN triatomics and their singly charged anions and cations. We used standard and explicitly correlated coupled cluster approaches in connection with large basis sets. At the highest levels of description, we show that results nicely approach those obtained at the complete basis set limit. Moreover, we generated the three-dimensional potential energy surfaces (3D PESs) for these molecular entities at the coupled cluster level with singles and doubles and a perturbative treatment of triple excitations, along with a basis set of augmented quintuple-zeta quality (aug-cc-pV5Z). A full set of spectroscopic constants are deduced from these potentials by applying perturbation theory. In addition, these 3D PESs are incorporated into variational treatment of the nuclear motions. The pattern of the lowest vibrational levels and corresponding wavefunctions, up to around 4000 cm{sup −1} above the corresponding potential energy minimum, is presented for the first time.

Inelastic vibrational bulk and surface losses of swift electrons in ionic nanostructures

Science.gov (United States)

Hohenester, Ulrich; Trügler, Andreas; Batson, Philip E.; Lagos, Maureen J.

2018-04-01

In a recent paper [Lagos et al., Nature (London) 543, 533 (2017), 10.1038/nature21699] we have used electron energy loss spectroscopy with sub-10 meV energy and atomic spatial resolution to map optical and acoustic, bulk and surface vibrational modes in magnesium oxide nanocubes. We found that a local dielectric description works well for the simulation of aloof geometries, similar to related work for surface plasmons and surface plasmon polaritons, while for intersecting geometries such a description fails to reproduce the rich spectral features associated with excitation of bulk acoustic and optical phonons. To account for scatterings with a finite momentum exchange, in this paper we investigate molecular and lattice dynamics simulations of bulk losses in magnesium-oxide nanocubes using a rigid-ion description and investigate the loss spectra for intersecting electron beams. From our analysis we can evaluate the capability of electron energy loss spectroscopy for the investigation of phonon modes at the nanoscale, and we discuss shortcomings of our simplified approach as well as directions for future investigations.

Optimizing hydroxyl airglow retrievals from long-slit astronomical spectroscopic observations

Directory of Open Access Journals (Sweden)

C. Franzen

2017-08-01

Full Text Available Astronomical spectroscopic observations from ground-based telescopes contain background emission lines from the terrestrial atmosphere's airglow. In the near infrared, this background is composed mainly of emission from Meinel bands of hydroxyl (OH, which is produced in highly excited vibrational states by reduction of ozone near 90 km. This emission contains a wealth of information on the chemical and dynamical state of the Earth's atmosphere. However, observation strategies and data reduction processes are usually optimized to minimize the influence of these features on the astronomical spectrum. Here we discuss a measurement technique to optimize the extraction of the OH airglow signal itself from routine J-, H-, and K-band long-slit astronomical spectroscopic observations. As an example, we use data recorded from a point-source observation by the Nordic Optical Telescope's intermediate-resolution spectrograph, which has a spatial resolution of approximately 100 m at the airglow layer. Emission spectra from the OH vibrational manifold from v′  =  9 down to v′  =  3, with signal-to-noise ratios up to 280, have been extracted from 10.8 s integrations. Rotational temperatures representative of the background atmospheric temperature near 90 km, the mesosphere and lower thermosphere region, can be fitted to the OH rotational lines with an accuracy of around 0.7 K. Using this measurement and analysis technique, we derive a rotational temperature distribution with v′ that agrees with atmospheric model conditions and the preponderance of previous work. We discuss the derived rotational temperatures from the different vibrational bands and highlight the potential for both the archived and future observations, which are at unprecedented spatial and temporal resolutions, to contribute toward the resolution of long-standing problems in atmospheric physics.

Interfacial instabilities in vibrated fluids

Science.gov (United States)

Porter, Jeff; Laverón-Simavilla, Ana; Tinao Perez-Miravete, Ignacio; Fernandez Fraile, Jose Javier

2016-07-01

Vibrations induce a range of different interfacial phenomena in fluid systems depending on the frequency and orientation of the forcing. With gravity, (large) interfaces are approximately flat and there is a qualitative difference between vertical and horizontal forcing. Sufficient vertical forcing produces subharmonic standing waves (Faraday waves) that extend over the whole interface. Horizontal forcing can excite both localized and extended interfacial phenomena. The vibrating solid boundaries act as wavemakers to excite traveling waves (or sloshing modes at low frequencies) but they also drive evanescent bulk modes whose oscillatory pressure gradient can parametrically excite subharmonic surface waves like cross-waves. Depending on the magnitude of the damping and the aspect ratio of the container, these locally generated surfaces waves may interact in the interior resulting in temporal modulation and other complex dynamics. In the case where the interface separates two fluids of different density in, for example, a rectangular container, the mass transfer due to vertical motion near the endwalls requires a counterflow in the interior region that can lead to a Kelvin-Helmholtz type instability and a ``frozen wave" pattern. In microgravity, the dominance of surface forces favors non-flat equilibrium configurations and the distinction between vertical and horizontal applied forcing can be lost. Hysteresis and multiplicity of solutions are more common, especially in non-wetting systems where disconnected (partial) volumes of fluid can be established. Furthermore, the vibrational field contributes a dynamic pressure term that competes with surface tension to select the (time averaged) shape of the surface. These new (quasi-static) surface configurations, known as vibroequilibria, can differ substantially from the hydrostatic state. There is a tendency for the interface to orient perpendicular to the vibrational axis and, in some cases, a bulge or cavity is induced

Ground test for vibration control demonstrator

Science.gov (United States)

Meyer, C.; Prodigue, J.; Broux, G.; Cantinaud, O.; Poussot-Vassal, C.

2016-09-01

In the objective of maximizing comfort in Falcon jets, Dassault Aviation is developing an innovative vibration control technology. Vibrations of the structure are measured at several locations and sent to a dedicated high performance vibration control computer. Control laws are implemented in this computer to analyse the vibrations in real time, and then elaborate orders sent to the existing control surfaces to counteract vibrations. After detailing the technology principles, this paper focuses on the vibration control ground demonstration that was performed by Dassault Aviation in May 2015 on Falcon 7X business jet. The goal of this test was to attenuate vibrations resulting from fixed forced excitation delivered by shakers. The ground test demonstrated the capability to implement an efficient closed-loop vibration control with a significant vibration level reduction and validated the vibration control law design methodology. This successful ground test was a prerequisite before the flight test demonstration that is now being prepared. This study has been partly supported by the JTI CleanSky SFWA-ITD.

Bonding and vibrational dynamics of a large π-conjugated molecule on a metal surface

International Nuclear Information System (INIS)

Temirov, R; Soubatch, S; Lassise, A; Tautz, F S

2008-01-01

The interplay between the substrate bonding of a large π-conjugated semiconductor molecule and the dynamical properties of the metal-organic interface is studied, employing the prototypical PTCDA/Ag(111) monolayer as an example. Both the coupling of molecular vibrations to the electron-hole-pair continuum of the metal surface and the inelastic scattering of tunnelling electrons by the molecular vibrations on their passage through the molecule are considered. The results of both types of experiment are consistent with the findings of measurements which probe the geometric and electronic structure of the adsorbate-substrate complex directly; generally speaking, they can be understood in the framework of standard theories for the electron-vibron coupling. While the experiments reported here in fact provide additional qualitative insights into the substrate bonding of our π-conjugated model molecule, their detailed quantitative understanding would require a full calculation of the dynamical interface properties, which is currently not available

Exploring Nuclear Photorelaxation of Pyranine in Aqueous Solution: an Integrated Ab-Initio Molecular Dynamics and Time Resolved Vibrational Analysis Approach.

Science.gov (United States)

Chiariello, Maria Gabriella; Rega, Nadia

2018-03-22

Advances in time-resolved vibrational spectroscopy techniques provided a new stimulus for understanding the transient molecular dynamics triggered by the electronic excitation. The detailed interpretation of such time-dependent spectroscopic signals is a challenging task from both experimental and theoretical points of view. We simulated and analyzed the transient photorelaxation of the pyranine photoacid in aqueous solution, with special focus on structural parameters and low frequency skeleton modes that are possibly preparatory for the photoreaction occurring at later time, as suggested by experimental spectroscopic studies. To this aim, we adopted an accurate computational protocol that combines excited state ab initio molecular dynamics within an hybrid quantum mechanical/molecular mechanics framework and a time-resolved vibrational analysis based on the Wavelet transform. According to our results, the main nuclear relaxation on the excited potential energy surface is completed in about 500 fs, in agreement with experimental data. The rearrangement of C-C bonds occurs according to a complex vibrational dynamics, showing oscillatory patterns that are out of phase and modulated by modes below 200 cm -1 . We also analyzed in both the ground and the excited state the evolution of some structural parameters involved in excited state proton transfer reaction, namely, those involving the pyranine and the water molecule hydrogen bonded to the phenolic O-H group. Both the hydrogen bond distance and the intermolecular orientation are optimized in the excited state, resulting in a tighter proton donor-acceptor couple. Indeed, we found evidence that collective low frequency skeleton modes, such as the out of plane wagging at 108 cm -1 and the deformation at 280 cm -1 , are photoactivated by the ultrafast part of the relaxation and modulate the pyranine-water molecule rearrangement, favoring the preparatory step for the photoreactivity.

SEM, EDS and vibrational spectroscopic study of dawsonite NaAl(CO3)(OH)2

Science.gov (United States)

Frost, Ray L.; López, Andrés; Scholz, Ricardo; Sampaio, Ney Pinheiro; de Oliveira, Fernando A. N.

2015-02-01

In this work we have studied the mineral dawsonite by using a combination of scanning electron microscopy with EDS and vibrational spectroscopy. Single crystals show an acicular habitus forming aggregates with a rosette shape. The chemical analysis shows a phase composed of C, Al, and Na. Two distinct Raman bands at 1091 and 1068 cm-1 are assigned to the CO32- ν1 symmetric stretching mode. Multiple bands are observed in both the Raman and infrared spectra in the antisymmetric stretching and bending regions showing that the symmetry of the carbonate anion is reduced and in all probability the carbonate anions are not equivalent in the dawsonite structure. Multiple OH deformation vibrations centred upon 950 cm-1 in both the Raman and infrared spectra show that the OH units in the dawsonite structure are non-equivalent. Raman bands observed at 3250, 3283 and 3295 cm-1 are assigned to OH stretching vibrations. The position of these bands indicates strong hydrogen bonding of the OH units in the dawsonite structure. The formation of the mineral dawsonite has the potential to offer a mechanism for the geosequestration of greenhouse gases.

Spectroscopic diagnostics of the vibrational population in the ground state of H2 and D2 molecules

International Nuclear Information System (INIS)

Fantz, U.; Heger, B.

1998-01-01

A diagnostic method has been evaluated for measuring the relative vibrational ground-state population of molecular hydrogen and deuterium. It is based on the analysis of the diagonal Fulcher bands · 3 Π u →a 3 Σ g + ) and the Franck-Condon principle of excitation. The validity of the underlying assumptions was verified by experiments in microwave discharges and the method is recommended for application in divertor plasmas in controlled fusion experiments. By attributing a vibrational temperature T vib to the ground-state electronic level (X 1 Σ g + ) and assuming population via the Franck-Condon principle, the upper Fulcher state vibrational distribution can be derived theoretically with T vib as parameter. Comparison with experimentally derived upper-state population gives the corresponding T vib of the ground state. The Franck-Condon factors for the · 3 Π 1 Σ g + and · 3 Π u →a 3 Σ g + transitions have been calculated for both hydrogen and deuterium from molecular constants using the FCFRKR code. The method has been applied to low pressure H 2 /He and D 2 /He microwave plasmas, showing good agreement of experimentally and theoretically derived upper Fulcher state vibrational distributions. The vibrational temperatures range from 3200 K to 6800 K for H 2 and 2600 K to 4000 K for D 2 · depending on molecular density, pressure and electron temperature, but indicating nearly the same vibrational population for H 2 and D 2 for comparable plasma conditions. (author)

In situ spectroscopic identification of neptunium(V) inner-sphere complexes on the hematite-water interface.

Science.gov (United States)

Müller, Katharina; Gröschel, Annett; Rossberg, André; Bok, Frank; Franzen, Carola; Brendler, Vinzenz; Foerstendorf, Harald

2015-02-17

Hematite plays a decisive role in regulating the mobility of contaminants in rocks and soils. The Np(V) reactions at the hematite-water interface were comprehensively investigated by a combined approach of in situ vibrational spectroscopy, X-ray absorption spectroscopy and surface complexation modeling. A variety of sorption parameters such as Np(V) concentration, pH, ionic strength, and the presence of bicarbonate was considered. Time-resolved IR spectroscopic sorption experiments at the iron oxide-water interface evidenced the formation of a single monomer Np(V) inner-sphere sorption complex. EXAFS provided complementary information on bidentate edge-sharing coordination. In the presence of atmospherically derived bicarbonate the formation of the bis-carbonato inner-sphere complex was confirmed supporting previous EXAFS findings.1 The obtained molecular structure allows more reliable surface complexation modeling of recent and future macroscopic data. Such confident modeling is mandatory for evaluating water contamination and for predicting the fate and migration of radioactive contaminants in the subsurface environment as it might occur in the vicinity of a radioactive waste repository or a reprocessing plant.

Raman spectroscopic studies of hydrogen clathrate hydrates.

Science.gov (United States)

Strobel, Timothy A; Sloan, E Dendy; Koh, Carolyn A

2009-01-07

Raman spectroscopic measurements of simple hydrogen and tetrahydrofuran+hydrogen sII clathrate hydrates have been performed. Both the roton and vibron bands illuminate interesting quantum dynamics of enclathrated H(2) molecules. The complex vibron region of the Raman spectrum has been interpreted by observing the change in population of these bands with temperature, measuring the absolute H(2) content as a function of pressure, and with D(2) isotopic substitution. Quadruple occupancy of the large sII clathrate cavity shows the highest H(2) vibrational frequency, followed by triple and double occupancies. Singly occupied small cavities display the lowest vibrational frequency. The vibrational frequencies of H(2) within all cavity environments are redshifted from the free gas phase value. At 76 K, the progression from ortho- to para-H(2) occurs over a relatively slow time period (days). The rotational degeneracy of H(2) molecules within the clathrate cavities is lifted, observed directly in splitting of the para-H(2) roton band. Raman spectra from H(2) and D(2) hydrates suggest that the occupancy patterns between the two hydrates are analogous, increasing confidence that D(2) is a suitable substitute for H(2). The measurements suggest that Raman is an effective and convenient method to determine the relative occupancy of hydrogen molecules in different clathrate cavities.

Vibrational spectroscopic and non-linear optical activity studies on nicotinanilide : A DFT approach

Science.gov (United States)

Premkumar, S.; Jawahar, A.; Mathavan, T.; Dhas, M. Kumara; Benial, A. Milton Franklin

2015-06-01

The molecular structure of nicotinanilide was optimized by the DFT/B3LYP method with cc-pVTZ basis set using Gaussian 09 program. The first order hyperpolarizability of the molecule was calculated, which exhibits the higher nonlinear optical activity. The natural bond orbital analysis confirms the presence of intramolecular charge transfer and the hydrogen bonding interaction, which leads to the higher nonlinear optical activity of the molecule. The Frontier molecular orbitals analysis of the molecule shows that the delocalization of electron density occurs within the molecule. The lower energy gap indicates that the hydrogen bond formation between the charged species. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation using the VEDA 4.0 program and the corresponding vibrational spectra were simulated. Hence, the nicotinanilide molecule can be a good candidate for second-order NLO material.

Effects of hydrogen peroxide bleaching strips on tooth surface color, surface microhardness, surface and subsurface ultrastructure, and microchemical (Raman spectroscopic) composition.

Science.gov (United States)

Duschner, Heinz; Götz, Hermann; White, Donald J; Kozak, Kathleen M; Zoladz, James R

2006-01-01

This study examined the effects of hydrogen peroxide tooth bleaching strips on the surface hardness and morphology of enamel and the ultrastructure and chemical composition of enamel and dentin in vitro. Sound human molars were ground and polished to prepare a uniform substrate for bleaching treatments. A cycling treatment methodology was employed which alternated ex vivo human salivary exposures with bleaching treatments under conditions of controlled temperature and durations of treatment. Bleaching treatments included commercial Crest Whitestrips bleaching strips, which utilize hydrogen peroxide in a gel as the in situ bleaching source at 6.0 and 6.5% concentrations of H2O2. Control treatments included an untreated group. Crest Whitestrips bleaching included treatment exposures simulating 2x the recommended clinical exposures (28 hours bleaching). Surface color measurements were taken prior to and following bleaching to ensure tooth bleaching activity. The effects of bleach on physical properties of enamel were assessed with microhardness measures. Ultrastructural effects were classified by surface and subsurface confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) techniques. In addition, the effects of bleaching on tooth microchemical composition was studied in different tooth regions by coincident assessment of Raman spectroscopic signature. Color assessments confirmed significant ex vivo tooth bleaching by Whitestrips. Surface microhardness and SEM measures revealed no deleterious effects on the enamel surfaces. CLSM micromorphological assessments supported the safety of hydrogen peroxide bleaching strips both on surface and subsurface enamel, DEJ, and dentin ultrastructure. Raman spectroscopy analysis demonstrated no obvious effects of bleaching treatments on the microchemical composition of enamel and dentin. These results confirm that tooth bleaching with hydrogen peroxide whitening strips does not produce changes in surface

Finite element modelling to assess the effect of surface mounted piezoelectric patch size on vibration response of a hybrid beam

Science.gov (United States)

Rahman, N.; Alam, M. N.

2018-02-01

Vibration response analysis of a hybrid beam with surface mounted patch piezoelectric layer is presented in this work. A one dimensional finite element (1D-FE) model based on efficient layerwise (zigzag) theory is used for the analysis. The beam element has eight mechanical and a variable number of electrical degrees of freedom. The beams are also modelled in 2D-FE (ABAQUS) using a plane stress piezoelectric quadrilateral element for piezo layers and a plane stress quadrilateral element for the elastic layers of hybrid beams. Results are presented to assess the effect of size of piezoelectric patch layer on the free and forced vibration responses of thin and moderately thick beams under clamped-free and clamped-clamped configurations. The beams are subjected to unit step loading and harmonic loading to obtain the forced vibration responses. The vibration control using in phase actuation potential on piezoelectric patches is also studied. The 1D-FE results are compared with the 2D-FE results.

Applying Low-Frequency Vibration for the Experimental Investigation of Clutch Hub Forming

Directory of Open Access Journals (Sweden)

De’an Meng

2018-05-01

Full Text Available A vibration-assisted plastic-forming method was proposed, and its influence on clutch hub forming process was investigated. The experiments were conducted on a vibration-assisted hydraulic extrusion press with adjustable frequency and amplitude. Vibration frequency and amplitude were considered in investigating the effect of vibration on forming load and surface quality. Results showed that applying vibration can effectively reduce forming force and improve surface quality. The drop in forming load was proportional to the vibration frequency and amplitude, and the load decreased by up to 25%. Such reduction in forming load raised with amplitude increase because the increase in amplitude would accelerate punch relative speed, which then weakened the adhesion between workpiece and dies. By increasing the vibration frequency, the punch movement was enhanced, and the number of attempts to drag the lubricant out of the pits was increased. In this manner, the lubrication condition was improved greatly. The 3D surface topography testing confirmed the assumption. Moreover, vibration frequency exerted a more significant effect on the forming load reduction than vibration amplitude.

Internal flow and evaporation characteristic inside a water droplet on a vertical vibrating hydrophobic surface

International Nuclear Information System (INIS)

Kim Hun; Lim, Hee Chang

2015-01-01

This study aims to understand the internal flow and the evaporation characteristics of a deionized water droplet subjected to vertical forced vibrations. To predict and evaluate its resonance frequency, the theories of Lamb, Strani, and Sabetta have been applied. To visualize the precise mode, shape, and internal flow inside a droplet, the experiment utilizes a combination of a high-speed camera, macro lens, and continuous laser. As a result, a water droplet on a hydrophobic surface has its typical shape at each mode, and complicated vortices are observed inside the droplet. In particular, large symmetrical flow streams are generated along the vertical axis at each mode, with a large circulating movement from the bottom to the top and then to the triple contact line along the droplet surface. In addition, a bifurcation-shaped flow pattern is formed at modes 2 and 4, whereas a large ellipsoid-shape flow pattern forms at modes 6 and 8. Mode 4 has the fastest internal flow speed and evaporation rate, followed by modes 8 then 6, with 2 having the slowest of these properties. Each mode has the fastest evaporation rate amongst its neighboring frequencies. Finally, the droplet evaporation under vertical vibration would lead to more rapid evaporation, particularly for mode 4

Internal flow and evaporation characteristic inside a water droplet on a vertical vibrating hydrophobic surface

Energy Technology Data Exchange (ETDEWEB)

Kim Hun; Lim, Hee Chang [School of Mechanical Engineering, Pusan National University, Busan (Korea, Republic of)

2015-07-15

This study aims to understand the internal flow and the evaporation characteristics of a deionized water droplet subjected to vertical forced vibrations. To predict and evaluate its resonance frequency, the theories of Lamb, Strani, and Sabetta have been applied. To visualize the precise mode, shape, and internal flow inside a droplet, the experiment utilizes a combination of a high-speed camera, macro lens, and continuous laser. As a result, a water droplet on a hydrophobic surface has its typical shape at each mode, and complicated vortices are observed inside the droplet. In particular, large symmetrical flow streams are generated along the vertical axis at each mode, with a large circulating movement from the bottom to the top and then to the triple contact line along the droplet surface. In addition, a bifurcation-shaped flow pattern is formed at modes 2 and 4, whereas a large ellipsoid-shape flow pattern forms at modes 6 and 8. Mode 4 has the fastest internal flow speed and evaporation rate, followed by modes 8 then 6, with 2 having the slowest of these properties. Each mode has the fastest evaporation rate amongst its neighboring frequencies. Finally, the droplet evaporation under vertical vibration would lead to more rapid evaporation, particularly for mode 4.

Vibrational spectroscopic study of dehydroacetic acid and its cinnamoyl pyrone derivatives

Science.gov (United States)

Billes, Ferenc; Elečková, Lenka; Mikosch, Hans; Andruch, Vasil

2015-07-01

The infrared and Raman spectra of dehydroacetic acid and some of its derivatives were measured. The assignments of the vibrational bands were based on quantum chemical calculations and normal coordinate analysis. The optimized structures, atomic net charges and dipole moments of the investigated molecules were also results of our quantum chemical calculations. The analysis of the last properties made possible a deeper insight into the structure and substituent effect on the investigated molecules. One of them is presented in the graphical abstract.

Sensor-Based Inspection of the Formation Accuracy in Ultra-Precision Grinding (UPG) of Aspheric Surface Considering the Chatter Vibration

Science.gov (United States)

Lei, Yao; Bai, Yue; Xu, Zhijun

2018-03-01

This paper proposes an experimental approach for monitoring and inspection of the formation accuracy in ultra-precision grinding (UPG) with respect to the chatter vibration. Two factors related to the grinding progress, the grinding speed of grinding wheel and spindle, and the oil pressure of the hydrostatic bearing are taken into account to determining the accuracy. In the meantime, a mathematical model of the radius deviation caused by the micro vibration is also established and applied in the experiments. The results show that the accuracy is sensitive to the vibration and the forming accuracy is much improved with proper processing parameters. It is found that the accuracy of aspheric surface can be less than 4 μm when the grinding speed is 1400 r/min and the wheel speed is 100 r/min with the oil pressure being 1.1 MPa.

Sensor-Based Inspection of the Formation Accuracy in Ultra-Precision Grinding (UPG) of Aspheric Surface Considering the Chatter Vibration

Science.gov (United States)

Lei, Yao; Bai, Yue; Xu, Zhijun

2018-06-01

This paper proposes an experimental approach for monitoring and inspection of the formation accuracy in ultra-precision grinding (UPG) with respect to the chatter vibration. Two factors related to the grinding progress, the grinding speed of grinding wheel and spindle, and the oil pressure of the hydrostatic bearing are taken into account to determining the accuracy. In the meantime, a mathematical model of the radius deviation caused by the micro vibration is also established and applied in the experiments. The results show that the accuracy is sensitive to the vibration and the forming accuracy is much improved with proper processing parameters. It is found that the accuracy of aspheric surface can be less than 4 μm when the grinding speed is 1400 r/min and the wheel speed is 100 r/min with the oil pressure being 1.1 MPa.

Experimental study on titanium wire drawing with ultrasonic vibration.

Science.gov (United States)

Liu, Shen; Shan, Xiaobiao; Guo, Kai; Yang, Yuancai; Xie, Tao

2018-02-01

Titanium and its alloys have been widely used in aerospace and biomedical industries, however, they are classified as difficult-to-machine materials. In this paper, ultrasonic vibration is imposed on the die to overcome the difficulties during conventional titanium wire drawing processes at the room temperature. Numerical simulations were performed to investigate the variation of axial stress within the contacting region and study the change of the drawing stress with several factors in terms of the longitudinal amplitude and frequency of the applied ultrasonic vibration, the diameter reduction ratio, and the drawing force. An experimental testing equipment was established to measure the drawing torque and rotational velocity of the coiler drum during the wire drawing process. The result indicates the drawing force increases with the growth of the drawing velocity and the reduction ratio, whether with or without vibrations. Application of either form of ultrasonic vibrations contributes to the further decrease of the drawing force, especially the longitudinal vibration with larger amplitude. SEM was employed to detect the surface morphology of the processed wires drawn under the three circumstances. The surface quality of the drawn wires with ultrasonic vibrations was apparently improved compared with those using conventional method. In addition, the longitudinal and torsional composite vibration was more effective for surface quality improvement than pure longitudinal vibration, however, at the cost of weakened drawing force reduction effect. Copyright © 2017 Elsevier B.V. All rights reserved.

FTIR and Raman spectroscopic studies of selenium nanoparticles synthesised by the bacterium Azospirillum thiophilum

Science.gov (United States)

Tugarova, Anna V.; Mamchenkova, Polina V.; Dyatlova, Yulia A.; Kamnev, Alexander A.

2018-03-01

Vibrational (Fourier transform infrared (FTIR) and Raman) spectroscopic techniques can provide unique molecular-level information on the structural and compositional characteristics of complicated biological objects. Thus, their applications in microbiology and related fields are steadily increasing. In this communication, biogenic selenium nanoparticles (Se NPs) were obtained via selenite (SeO32-) reduction by the bacterium Azospirillum thiophilum (strain VKM B-2513) for the first time, using an original methodology for obtaining extracellular NPs. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) showed the Se NPs to have average diameters within 160-250 nm; their zeta potential was measured to be minus 18.5 mV. Transmission FTIR spectra of the Se NPs separated from bacterial cells showed typical proteinacious, polysaccharide and lipid-related bands, in line with TEM data showing a thin layer covering the Se NPs surface. Raman spectra of dried Se NPs layer in the low-frequency region (under 500 cm-1 down to 150 cm-1) showed a single very strong band with a maximum at 250 cm-1 which, in line with its increased width (ca. 30 cm-1 at half intensity), can be attributed to amorphous elementary Se. Thus, a combination of FTIR and Raman spectroscopic approaches is highly informative in non-destructive analysis of structural and compositional properties of biogenic Se NPs.

The sorption of uranium(VI) and neptunium(V) onto surfaces of selected metal oxides and alumosilicates studied by in situ vibrational spectroscopy

International Nuclear Information System (INIS)

Mueller, Katharina

2010-05-01

(VI). For both actinides, the formation of similar species is suggested at pH ≤ 4, whereas at higher pH, the infrared spectra evidence structurally different species. At pH 5, the formation of a carbonate-containing dimeric complex, that is (NpO 2 ) 2 CO 3 (OH) 3 - , is strongly suggested, whereas carbonate complexation occurs only under more alkaline conditions in the U(VI) system. The results from the experiments of the sorption processes clearly demonstrate the formation of stable U(VI) surface complexes at all investigated mineral phases. This includes several metal oxides, namely TiO 2 , Al 2 O 3 , and SiO 2 , serving as model systems for the elucidation of more complex mineral systems, and several alumosilicates, such as kaolinite, muscovite and biotite. From a multiplicity of in situ experiments, the impact of sorbent characteristics and variations in the aqueous U(VI) system on the sorption processes was considered. A preferential formation of an inner-sphere complex is derived from the spectra of the TiO 2 and SiO 2 phases. In addition, since the in situ FT-IR experiments provide an online monitoring of the absorption changes of the sorption processes, the course of the formation of the U(VI) surface complexes can be observed spectroscopically. It is shown that after prolonged sorption time on TiO 2 , resulting in a highly covered surface, outer-sphere complexation predominates the sorption processes. The prevailing crystallographic modification, namely anatase and rutile, does not significantly contribute to the spectra, whereas surface specific parameters, e.g. surface area or porosity are important. A significant different surface complexation is observed for Al 2 O 3 . The formation of innerspheric species is assumed at low U(VI) surface coverage which is fostered at low pH, high ionic strength and short contact times. At proceeded sorption the surface complexation changes. From the spectra, an outer-spheric coordination followed by surface precipitation or

Local-mode vibrations of water

International Nuclear Information System (INIS)

Lawton, R.T.; Child, M.S.

1981-01-01

Quantum-mechanical eigenvalues for the stretching vibrations of H 2 O on the Sorbie-Murrell potential surface are shown to contain a series of local-mode doublets, with splittings which vary as the energy increases from 100 cm - 1 at v=1 to 0.001 cm - 1 at v=8. Preliminary calculations indicate that this pattern is largely unaffected by inclusion of the bending vibrational mode. (author)

Moving contact lines on vibrating surfaces

Science.gov (United States)

Solomenko, Zlatko; Spelt, Peter; Scott, Julian

2017-11-01

Large-scale simulations of flows with moving contact lines for realistic conditions generally requires a subgrid scale model (analyses based on matched asymptotics) to account for the unresolved part of the flow, given the large range of length scales involved near contact lines. Existing models for the interface shape in the contact-line region are primarily for steady flows on homogeneous substrates, with encouraging results in 3D simulations. Introduction of complexities would require further investigation of the contact-line region, however. Here we study flows with moving contact lines on planar substrates subject to vibrations, with applications in controlling wetting/dewetting. The challenge here is to determine the change in interface shape near contact lines due to vibrations. To develop further insight, 2D direct numerical simulations (wherein the flow is resolved down to an imposed slip length) have been performed to enable comparison with asymptotic theory, which is also developed further. Perspectives will also be presented on the final objective of the work, which is to develop a subgrid scale model that can be utilized in large-scale simulations. The authors gratefully acknowledge the ANR for financial support (ANR-15-CE08-0031) and the meso-centre FLMSN for use of computational resources. This work was Granted access to the HPC resources of CINES under the allocation A0012B06893 made by GENCI.

Carrier dynamics and surface vibration-assisted Auger recombination in porous silicon

Science.gov (United States)

Zakar, Ammar; Wu, Rihan; Chekulaev, Dimitri; Zerova, Vera; He, Wei; Canham, Leigh; Kaplan, Andrey

2018-04-01

Excitation and recombination dynamics of the photoexcited charge carriers in porous silicon membranes were studied using a femtosecond pump-probe technique. Near-infrared pulses (800 nm, 60 fs) were used for the pump while, for the probe, we employed different wavelengths in the range between 3.4 and 5 μ m covering the medium wavelength infrared range. The data acquired in these experiments consist of simultaneous measurements of the transmittance and reflectance as a function of the delay time between the pump and probe for different pump fluences and probe wavelengths. To evaluate the results, we developed an optical model based on the two-dimensional Maxwell-Garnett formula, incorporating the free-carrier Drude contribution and nonuniformity of the excitation by the Wentzel-Kramers-Brillouin model. This model allowed the retrieval of information about the carrier density as a function of the pump fluence, time, and wavelength. The carrier density data were analyzed to reveal that the recombination dynamics is governed by Shockley-Read-Hall and Auger processes, whereas the diffusion has an insignificant contribution. We show that, in porous silicon samples, the Auger recombination process is greatly enhanced at the wavelength corresponding to the infrared-active vibrational modes of the molecular impurities on the surface of the pores. This observation of surface-vibration-assisted Auger recombination is not only for porous silicon in particular, but for low-dimension and bulk semiconductors in general. We estimate the time constants of Shockley-Read-Hall and Auger processes, and demonstrate their wavelength dependence for the excited carrier density in the range of 1018-10191 /cm3 . We demonstrate that both processes are enhanced by up to three orders of magnitude with respect to the bulk counterpart. In addition, we provide a plethora of the physical parameters evaluated from the experimental data, such as the dielectric function and its dependence on the

Vibrations of a molecule in an external force field.

Science.gov (United States)

Okabayashi, Norio; Peronio, Angelo; Paulsson, Magnus; Arai, Toyoko; Giessibl, Franz J

2018-05-01

The oscillation frequencies of a molecule on a surface are determined by the mass distribution in the molecule and the restoring forces that occur when the molecule bends. The restoring force originates from the atomic-scale interaction within the molecule and with the surface, which plays an essential role in the dynamics and reactivity of the molecule. In 1998, a combination of scanning tunneling microscopy with inelastic tunneling spectroscopy revealed the vibrational frequencies of single molecules adsorbed on a surface. However, the probe tip itself exerts forces on the molecule, changing its oscillation frequencies. Here, we combine atomic force microscopy with inelastic tunneling spectroscopy and measure the influence of the forces exerted by the tip on the lateral vibrational modes of a carbon monoxide molecule on a copper surface. Comparing the experimental data to a mechanical model of the vibrating molecule shows that the bonds within the molecule and with the surface are weakened by the proximity of the tip. This combination of techniques can be applied to analyze complex molecular vibrations and the mechanics of forming and loosening chemical bonds, as well as to study the mechanics of bond breaking in chemical reactions and atomic manipulation.

Thermal analysis and vibrational spectroscopic characterization of the boro silicate mineral datolite - CaBSiO4(OH)

Science.gov (United States)

Frost, Ray L.; Xi, Yunfei; Scholz, Ricardo; Lima, Rosa Malena Fernandes; Horta, Laura Frota Campos; Lopez, Andres

2013-11-01

The objective of this work is to determine the thermal stability and vibrational spectra of datolite CaBSiO4(OH) and relate these properties to the structure of the mineral. The thermal analysis of datolite shows a mass loss of 5.83% over a 700-775 °C temperature range. This mass loss corresponds to 1 water (H2O) molecules pfu. A quantitative chemical analysis using electron probe was undertaken. The Raman spectrum of datolite is characterized by bands at 917 and 1077 cm-1 assigned to the symmetric stretching modes of BO and SiO tetrahedra. A very intense Raman band is observed at 3498 cm-1 assigned to the stretching vibration of the OH units in the structure of datolite. BOH out-of-plane vibrations are characterized by the infrared band at 782 cm-1. The vibrational spectra are based upon the structure of datolite based on sheets of four- and eight-membered rings of alternating SiO4 and BO3(OH) tetrahedra with the sheets bonded together by calcium atoms.

FTIR and Vis-FUV real time spectroscopic ellipsometry studies of polymer surface modifications during ion beam bombardment

Science.gov (United States)

Laskarakis, A.; Gravalidis, C.; Logothetidis, S.

2004-02-01

The continuously increasing application of polymeric materials in many scientific and technological fields has motivated an extensive use of polymer surface treatments, which modify the physical and chemical properties of polymer surfaces leading to surface activation and promotion of the surface adhesion. Fourier transform IR spectroscopic ellipsometry (FTIRSE) and phase modulated ellipsometry (PME) in the IR and Vis-FUV spectral regions respectively have been employed for in situ and real time monitoring of the structural changes on the polymer surface obtained by Ar + ion bombardment. The polymers were industrially supplied polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) membranes. The Ar + ion bombardment has found to change the chemical bonding of the films and especially the amount of the CO, C-C and CC groups. The detailed study of the FTIRSE spectra reveals important information about the effect of the Ar + ion bombardment on each of the above bonding groups. Also, the modification of the characteristic features, attributed to electronic transitions in specific bonds of PET and PEN macromolecules, has been studied using PME.

FTIR and Vis-FUV real time spectroscopic ellipsometry studies of polymer surface modifications during ion beam bombardment

International Nuclear Information System (INIS)

Laskarakis, A.; Gravalidis, C.; Logothetidis, S.

2004-01-01

The continuously increasing application of polymeric materials in many scientific and technological fields has motivated an extensive use of polymer surface treatments, which modify the physical and chemical properties of polymer surfaces leading to surface activation and promotion of the surface adhesion. Fourier transform IR spectroscopic ellipsometry (FTIRSE) and phase modulated ellipsometry (PME) in the IR and Vis-FUV spectral regions respectively have been employed for in situ and real time monitoring of the structural changes on the polymer surface obtained by Ar + ion bombardment. The polymers were industrially supplied polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) membranes. The Ar + ion bombardment has found to change the chemical bonding of the films and especially the amount of the C-O, C-C and C-C groups. The detailed study of the FTIRSE spectra reveals important information about the effect of the Ar + ion bombardment on each of the above bonding groups. Also, the modification of the characteristic features, attributed to electronic transitions in specific bonds of PET and PEN macromolecules, has been studied using PME

Resonant and kinematical enhancement of He scattering from LiF(001) surface and pseudosurface vibrational normal modes

International Nuclear Information System (INIS)

Nichols, W.L.; Weare, J.H.

1986-01-01

One-phonon cross sections calculated from sagittally polarized vibrational normal modes account for most salient inelastic-scattering intensities seen in He-LiF(001) and measurements published by Brusdeylins, Doak, and Toennies. We have found that most inelastic intensities which cannot be attributed to potential resonances can be explained as kinematically enhanced scattering from both surface and pseudosurface bulk modes

Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations

Science.gov (United States)

Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

2015-04-01

A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of Carbamazepine.

Amplification of an Autodyne Signal in a Bistable Vertical-Cavity Surface-Emitting Laser with the Use of a Vibrational Resonance

Science.gov (United States)

Chizhevsky, V. N.

2018-01-01

For the first time, it is demonstrated experimentally that a vibrational resonance in a polarization-bistable vertical-cavity surface-emitting laser can be used to increase the laser response in autodyne detection of microvibrations from reflecting surfaces. In this case, more than 25-fold signal amplification is achieved. The influence of the asymmetry of the bistable potential on the microvibration-detection efficiency is studied.

Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

Science.gov (United States)

Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

2018-06-01

Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.

Principles of Vibrational Spectroscopic Methods and their Application to Bioanalysis

DEFF Research Database (Denmark)

Moore, David S.; Jepsen, Peter Uhd; Volka, Karel

2014-01-01

imaging, fiber optic probes for in vivo and in vitro analysis, and methods to obtain depth profile information. The issue of fluorescence interference will be considered from the perspectives of excitation wavelength selection and data treatment. Methods to optimize signal to noise with minimized...... excitation laser irradiance to avoid sample damage are also discussed. This chapter then reviews applications of Raman spectroscopy to bioanalysis. Areas discussed include pathology, cytopathology, single-cell analysis, in vivo and in vitro tissue characterization, chemical composition of cell components...... as conformation of DNA and proteins), vibrations of inter- and intramolecular hydrogen bonds in solid-state materials, as well as picosecond dynamics in liquid solutions. This chapter reviews modern instrumentation and techniques for THz spectroscopy, with emphasis on applications in bioanalysis....

Calculation of acoustic field based on laser-measured vibration velocities on ultrasonic transducer surface

Science.gov (United States)

Hu, Liang; Zhao, Nannan; Gao, Zhijian; Mao, Kai; Chen, Wenyu; Fu, Xin

2018-05-01

Determination of the distribution of a generated acoustic field is valuable for studying ultrasonic transducers, including providing the guidance for transducer design and the basis for analyzing their performance, etc. A method calculating the acoustic field based on laser-measured vibration velocities on the ultrasonic transducer surface is proposed in this paper. Without knowing the inner structure of the transducer, the acoustic field outside it can be calculated by solving the governing partial differential equation (PDE) of the field based on the specified boundary conditions (BCs). In our study, the BC on the transducer surface, i.e. the distribution of the vibration velocity on the surface, is accurately determined by laser scanning measurement of discrete points and follows a data fitting computation. In addition, to ensure the calculation accuracy for the whole field even in an inhomogeneous medium, a finite element method is used to solve the governing PDE based on the mixed BCs, including the discretely measured velocity data and other specified BCs. The method is firstly validated on numerical piezoelectric transducer models. The acoustic pressure distributions generated by a transducer operating in an homogeneous and inhomogeneous medium, respectively, are both calculated by the proposed method and compared with the results from other existing methods. Then, the method is further experimentally validated with two actual ultrasonic transducers used for flow measurement in our lab. The amplitude change of the output voltage signal from the receiver transducer due to changing the relative position of the two transducers is calculated by the proposed method and compared with the experimental data. This method can also provide the basis for complex multi-physical coupling computations where the effect of the acoustic field should be taken into account.

A Comparative Study of Ground and Underground Vibrations Induced by Bench Blasting

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Xiuzhi Shi

2016-01-01

Full Text Available Ground vibrations originating from bench blasting may cause damage to slopes, structures, and underground workings in close proximity to an operating open-pit mine. It is important to monitor and predict ground vibration levels induced by blasting and to take measures to reduce their hazardous effects. The aims of this paper are to determine the weaker protection objects by comparatively studying bench blasting induced vibrations obtained at surface and in an underground tunnel in an open-pit mine and thus to seek vibration control methods to protect engineering objects at the site. Vibrations arising from measurement devices at surface and in an underground tunnel at the Zijinshan Open-Pit Mine were obtained. Comparative analysis of the peak particle velocities shows that, in the greatest majority of cases, surface values are higher than underground values for the same vibration distance. The transmission laws of surface and underground vibrations were established depending on the type of rock mass, the explosive charge, and the distance. Compared with the Chinese Safety Regulations for Blasting (GB6722-2014, the bench blasting induced vibrations would not currently cause damage to the underground tunnel. According to the maximum allowable peak particle velocities for different objects, the permitted maximum charges per delay are obtained to reduce damage to these objects at different distances.

Crystal structure and vibrational spectra of melaminium arsenate

Science.gov (United States)

Anbalagan, G.; Marchewka, M. K.; Pawlus, K.; Kanagathara, N.

2015-01-01

The crystals of the new melaminium arsenate (MAS) [C3H7N6+ṡH2AsO4-] were obtained by the slow evaporation of an aqueous solution at room temperature. Single crystal X-ray diffraction analysis reveals that the crystal belongs to triclinic system with centro symmetric space group P-1. The crystals are built up from single protonated melaminium residues and single dissociated arsenate H2AsO4- anions. The protonated melaminium ring is almost planar. A combination of ionic and donor-acceptor hydrogen-bond interactions linking together the melaminium and arsenate residues forms a three-dimensional network. Vibrational spectroscopic analysis is reported on the basis of FT-IR and FT-Raman spectra recorded at room temperature. Hydrogen bonded network present in the crystal gives notable vibrational effect. DSC has also been performed for the crystal shows no phase transition in the studied temperature range (113-293 K).

DFT, FT-IR, FT-Raman and vibrational studies of 3-methoxyphenyl boronic acid

Science.gov (United States)

Patil, N. R.; Hiremath, Sudhir M.; Hiremath, C. S.

2018-05-01

The aim of this work is to study the possible stable, geometrical molecular structure, experimental and theoretical FT-IR and FT-Raman spectroscopic methods of 3-Methoxyphenyl boronic acid (3MPBA). FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1 and 40000-50 cm-1 respectively. The optimized geometric structure and vibrational wavenumbers of the title compound were searched by B3LYP hybrid density functional theory method with 6-311++G (d, p) basis set. The Selectedexperimentalbandswereassignedandcharacterizedonthebasisofthescaledtheoreticalwavenumbersby their potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. Finally, the predicted calculation results were applied to simulated FT-IR and FT-Raman spectra of the title compound, which show agreement with the observed spectra. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

Local-mode vibrations of water

Energy Technology Data Exchange (ETDEWEB)

Lawton, R.T.; Child, M.S. (Oxford Univ. (UK). Dept. of Theoretical Chemistry)

1981-05-11

Quantum-mechanical eigenvalues for the stretching vibrations of H/sub 2/O on the Sorbie-Murrell potential surface are shown to contain a series of local-mode doublets, with splittings which vary as the energy increases from 100 cm/sup -1/ at v=1 to 0.001 cm/sup -1/ at v=8. Preliminary calculations indicate that this pattern is largely unaffected by inclusion of the bending vibrational mode.

Local-mode vibrations of water

Energy Technology Data Exchange (ETDEWEB)

Lawton, R.T.; Child, M.S. (Oxford Univ. (UK). Dept. of Theoretical Chemistry)

1981-05-11

Quantum-mechanical eigenvalues for the stretching vibrations of H/sub 2/O on the Sorbie-Murrell potential surface are shown to contain a series of local-mode doublets, with splittings which vary as the energy increases from 100 cm/sup -1/ at theta=1 to 0.001 cm/sup -1/ at theta=8. Preliminary calculations indicate that this pattern is largely unaffected by inclusion of the bending vibrational mode.

Vibrational deactivation on chemically reactive potential surfaces: An exact quantum study of a low barrier collinear model of H + FH, D + FD, H + FD and D + FH

International Nuclear Information System (INIS)

Schatz, G.C.; Kuppermann, A.

1980-01-01

We study vibrational deactivation processes on chemically reactive potential energy surfaces by examining accurate quantum mechanical transition probabilities and rate constants for the collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) reactions. A low barrier (1.7 kcal/mole) potential surface is used in these calculations, and we find that for all four reactions, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states. However, the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and the isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a low barrier reactive surface, and can make chemically reactive atoms like H or D more efficient deactivators of HF or DF than nonreactive collision partners. Many conclusions are in at least qualitative agreement with those of Wilkin's three dimensional quasiclassical trajectory study on the same systems using a similar surface. We also present results for H + HF(v) collisions which show that for a higher barrier potential surface (33 rather than 1.7 kcal/mole), the deactivation process becomes similar in character to that for nonreactive partners, with v→v-1 processes dominating

Vibrational and UV spectroscopic studies of 2-coumaranone by experimental and density functional theory calculations

Science.gov (United States)

Priya, Y. Sushma; Rao, K. Ramachandra; Chalapathi, P. V.; Satyavani, M.; Veeraiah, A.

2017-09-01

The vibrational and electronic properties of 2-coumaranone have been reported in the ground state using experimental techniques (FT-IR, FT-Raman, UV spectra and fluorescence microscopic imaging) and density functional theory (DFT) employing B3LYP correlation with the 6-31G(d, p) basis set. The theoretically reported optimized parameters, vibrational frequencies etc., were compared with the experimental values, which yielded good concurrence between the experimental and calculated values. The assignments of the vibrational spectra were done with the help of normal co-ordinate analysis (NCA) following the Scaled Quantum Mechanical Force Field(SQMFF) methodology. The whole assignments of fundamental modes were based on the potential energy distribution (PED) matrix. The electric dipole moment and the first order hyperpolarizability of the 2-coumaranone have been computed using quantum mechanical calculations. NBO and HOMO, LUMO analyses have been carried out. UV spectrum of 2-coumaranone was recorded in the region 100-300 nm and compared with the theoretical UV spectrum using TD-DFT and SAC-CI methods by which a good agreement is observed. Fluorescence microscopic imaging study reflects that the compound fluoresces in the green-yellow region.

Molecular structure, chemical reactivity, nonlinear optical activity and vibrational spectroscopic studies on 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one: A combined density functional theory and experimental approach

Science.gov (United States)

Pegu, David; Deb, Jyotirmoy; Saha, Sandip Kumar; Paul, Manoj Kumar; Sarkar, Utpal

2018-05-01

In this work, we have synthesized new coumarin Schiff base molecule, viz., 6-(4-n-heptyloxybenzyoloxy)-2-hydroxybenzylidene)amino)-2H-chromen-2-one and characterized its structural, electronic and spectroscopic properties experimentally and theoretically. The theoretical analysis of UV-visible absorption spectra reflects a red shift in the absorption maximum in comparison to the experimental results. Most of the vibrational assignments of infrared and Raman spectra predicted using density functional theory approach match well with the experimental findings. Further, the chemical reactivity analysis confirms that solvent highly affects the reactivity of the studied compound. The large hyperpolarizability value of the compound concludes that the system exhibits significant nonlinear optical features and thus, points out their possibility in designing material with high nonlinear activity.

Circularly polarized infrared and visible sum-frequency-generation spectroscopy: Vibrational optical activity measurement

International Nuclear Information System (INIS)

Cheon, Sangheon; Cho, Minhaeng

2005-01-01

Vibrational optical activity spectroscopies utilizing either circularly polarized ir or circularly polarized visible beams were theoretically investigated by considering the infrared and visible sum-frequency-generation (IV-SFG) schemes. In addition to the purely electric dipole-allowed chiral component of the IV-SFG susceptibility, the polarizability-electric quadrupole hyperpolarizability term also contributes to the vibrationally resonant IV-SFG susceptibility. The circular-intensity-difference signal is shown to be determined by the interferences between the all-electric dipole-allowed chiral component and the polarizability-electric-dipole or electric-dipole-electric-quadrupole Raman optical activity tensor components. The circularly polarized SFG methods are shown to be potentially useful coherent spectroscopic tools for determining absolute configurations of chiral molecules in condensed phases

Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS)

Science.gov (United States)

Wang, Hong-Fei; Gan, Wei; Lu, Rong; Rao, Yi; Wu, Bao-Hua

Sum frequency generation vibrational spectroscopy (SFG-VS) has been proven to be a uniquely effective spectroscopic technique in the investigation of molecular structure and conformations, as well as the dynamics of molecular interfaces. However, the ability to apply SFG-VS to complex molecular interfaces has been limited by the ability to abstract quantitative information from SFG-VS experiments. In this review, we try to make assessments of the limitations, issues and techniques as well as methodologies in quantitative orientational and spectral analysis with SFG-VS. Based on these assessments, we also try to summarize recent developments in methodologies on quantitative orientational and spectral analysis in SFG-VS, and their applications to detailed analysis of SFG-VS data of various vapour/neat liquid interfaces. A rigorous formulation of the polarization null angle (PNA) method is given for accurate determination of the orientational parameter D = /, and comparison between the PNA method with the commonly used polarization intensity ratio (PIR) method is discussed. The polarization and incident angle dependencies of the SFG-VS intensity are also reviewed, in the light of how experimental arrangements can be optimized to effectively abstract crucial information from the SFG-VS experiments. The values and models of the local field factors in the molecular layers are discussed. In order to examine the validity and limitations of the bond polarizability derivative model, the general expressions for molecular hyperpolarizability tensors and their expression with the bond polarizability derivative model for C3v, C2v and C∞v molecular groups are given in the two appendixes. We show that the bond polarizability derivative model can quantitatively describe many aspects of the intensities observed in the SFG-VS spectrum of the vapour/neat liquid interfaces in different polarizations. Using the polarization analysis in SFG-VS, polarization selection rules or

Towards vibrational spectroscopy on surface-attached colloids performed with a quartz crystal microbalance

Directory of Open Access Journals (Sweden)

Diethelm Johannsmann

2016-12-01

Full Text Available Colloidal spheres attached to a quartz crystal microbalance (QCM produce the so-called “coupled resonances”. They are resonators of their own, characterized by a particle resonance frequency, a resonance bandwidth, and a modal mass. When the frequency of the main resonator comes close to the frequency of the coupled resonance, the bandwidth goes through a maximum. A coupled resonance can be viewed as an absorption line in acoustic shear-wave spectroscopy. The known concepts from spectroscopy apply. This includes the mode assignment problem, selection rules, and the oscillator strength. In this work, the mode assignment problem was addressed with Finite Element calculations. These reveal that a rigid sphere in contact with a QCM displays two modes of vibration, termed “slipping” and “rocking”. In the slipping mode, the sphere rotates about its center; it exerts a tangential force onto the resonator surface at the point of contact. In the rocking mode, the sphere rotates about the point of contact; it exerts a torque onto the substrate. In liquids, both axes of rotation are slightly displaced from their ideal positions. Characteristic for spectroscopy, the two modes do not couple to the mechanical excitation equally well. The degree of coupling is quantified by an oscillator strength. Because the rocking mode mostly exerts a torque (rather than a tangential force, its coupling to the resonator's tangential motion is weak; the oscillator strength consequently is small. Recent experiments on surface-adsorbed colloidal spheres can be explained by the mode of vibration being of the rocking type. Keywords: Quartz crystal microbalance, Coupled resonance, Biocolloids, Adsorption

Method and apparatus for vibrating a substrate during material formation

Science.gov (United States)

Bailey, Jeffrey A [Richland, WA; Roger, Johnson N [Richland, WA; John, Munley T [Benton City, WA; Walter, Park R [Benton City, WA

2008-10-21

A method and apparatus for affecting the properties of a material include vibrating the material during its formation (i.e., "surface sifting"). The method includes the steps of providing a material formation device and applying a plurality of vibrations to the material during formation, which vibrations are oscillations having dissimilar, non-harmonic frequencies and at least two different directions. The apparatus includes a plurality of vibration sources that impart vibrations to the material.

Computational Fluid Dynamic Analysis of a Vibrating Turbine Blade

Directory of Open Access Journals (Sweden)

Osama N. Alshroof

2012-01-01

Full Text Available This study presents the numerical fluid-structure interaction (FSI modelling of a vibrating turbine blade using the commercial software ANSYS-12.1. The study has two major aims: (i discussion of the current state of the art of modelling FSI in gas turbine engines and (ii development of a “tuned” one-way FSI model of a vibrating turbine blade to investigate the correlation between the pressure at the turbine casing surface and the vibrating blade motion. Firstly, the feasibility of the complete FSI coupled two-way, three-dimensional modelling of a turbine blade undergoing vibration using current commercial software is discussed. Various modelling simplifications, which reduce the full coupling between the fluid and structural domains, are then presented. The one-way FSI model of the vibrating turbine blade is introduced, which has the computational efficiency of a moving boundary CFD model. This one-way FSI model includes the corrected motion of the vibrating turbine blade under given engine flow conditions. This one-way FSI model is used to interrogate the pressure around a vibrating gas turbine blade. The results obtained show that the pressure distribution at the casing surface does not differ significantly, in its general form, from the pressure at the vibrating rotor blade tip.

Quantitative Surface Chirality Detection with Sum Frequency Generation Vibrational Spectroscopy: Twin Polarization Angle Approach

International Nuclear Information System (INIS)

Wei, Feng; Xu, Yanyan; Guo, Yuan; Liu, Shi-lin; Wang, Hongfei

2009-01-01

Here we report a novel twin polarization angle (TPA) approach in the quantitative chirality detection with the surface sum-frequency generation vibrational spectroscopy (SFG-VS). Generally, the achiral contribution dominates the surface SFG-VS signal, and the pure chiral signal is usually two or three orders of magnitude smaller. Therefore, it has been difficult to make quantitative detection and analysis of the chiral contributions to the surface SFG-VS signal. In the TPA method, by varying together the polarization angles of the incoming visible light and the sum frequency signal at fixed s or p polarization of the incoming infrared beam, the polarization dependent SFG signal can give not only direct signature of the chiral contribution in the total SFG-VS signal, but also the accurate measurement of the chiral and achiral components in the surface SFG signal. The general description of the TPA method is presented and the experiment test of the TPA approach is also presented for the SFG-VS from the S- and R-limonene chiral liquid surfaces. The most accurate degree of chiral excess values thus obtained for the 2878 cm -1 spectral peak of the S- and R-limonene liquid surfaces are (23.7±0.4)% and (25.4±1.3)%, respectively.

Vibration-Induced Climbing of Drops

Science.gov (United States)

Brunet, P.; Eggers, J.; Deegan, R. D.

2007-10-01

We report an experimental study of liquid drops moving against gravity, when placed on a vertically vibrating inclined plate, which is partially wetted by the drop. The frequency of vibrations ranges from 30 to 200 Hz, and, above a threshold in vibration acceleration, drops experience an upward motion. We attribute this surprising motion to the deformations of the drop, as a consequence of an up or down symmetry breaking induced by the presence of the substrate. We relate the direction of motion to contact angle measurements. This phenomenon can be used to move a drop along an arbitrary path in a plane, without special surface treatments or localized forcing.

Spectroscopic Parameter and Molecular Constant Investigations on Low-Lying States of BeF Radical

Directory of Open Access Journals (Sweden)

Jin Feng Sun

2012-02-01

Full Text Available The potential energy curves (PECs of X2Σ+, A2Πr and B2Σ+ states of BeF radical have been investigated using the complete active space self-consistent-field (CASSCF method, followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI approach at the correlation-consistent basis sets, cc-pV5Z for Be and aug-cc-pV6Z for F. Based on the PECs of X2Σ+, A2Πr and B2Σ+ states, the spectroscopic parameters (De, Re, ωe, ωeχe, αe and Be have also been determined in the present work. With the PECs determined at the present level of theory, vibrational states have been predicted for each state when the rotational quantum number J equals zero (J = 0. The vibrational levels, inertial rotation and centrifugal distortion constants are determined for the three states, and the classical turning points are also calculated for the X2Σ+ state. Compared with the available experiments and other theories, it can be seen that the present spectroscopic parameter and molecular constant results are more fully in agreement with the experimental findings.

Neural networks vs Gaussian process regression for representing potential energy surfaces: A comparative study of fit quality and vibrational spectrum accuracy

Science.gov (United States)

Kamath, Aditya; Vargas-Hernández, Rodrigo A.; Krems, Roman V.; Carrington, Tucker; Manzhos, Sergei

2018-06-01

For molecules with more than three atoms, it is difficult to fit or interpolate a potential energy surface (PES) from a small number of (usually ab initio) energies at points. Many methods have been proposed in recent decades, each claiming a set of advantages. Unfortunately, there are few comparative studies. In this paper, we compare neural networks (NNs) with Gaussian process (GP) regression. We re-fit an accurate PES of formaldehyde and compare PES errors on the entire point set used to solve the vibrational Schrödinger equation, i.e., the only error that matters in quantum dynamics calculations. We also compare the vibrational spectra computed on the underlying reference PES and the NN and GP potential surfaces. The NN and GP surfaces are constructed with exactly the same points, and the corresponding spectra are computed with the same points and the same basis. The GP fitting error is lower, and the GP spectrum is more accurate. The best NN fits to 625/1250/2500 symmetry unique potential energy points have global PES root mean square errors (RMSEs) of 6.53/2.54/0.86 cm-1, whereas the best GP surfaces have RMSE values of 3.87/1.13/0.62 cm-1, respectively. When fitting 625 symmetry unique points, the error in the first 100 vibrational levels is only 0.06 cm-1 with the best GP fit, whereas the spectrum on the best NN PES has an error of 0.22 cm-1, with respect to the spectrum computed on the reference PES. This error is reduced to about 0.01 cm-1 when fitting 2500 points with either the NN or GP. We also find that the GP surface produces a relatively accurate spectrum when obtained based on as few as 313 points.

A Study of Polishing Feature of Ultrasonic-Assisted Vibration Method in Bamboo Charcoal

Directory of Open Access Journals (Sweden)

Hsin-Min Lee

2017-01-01

Full Text Available Focusing on the feature of porosity in bamboo charcoal, this study applies the ultrasonic-assisted vibration method to perform surface polishing of the silicon wafer workpiece. The self-developed bamboo charcoal polishing spindle and ultrasonic- assisted vibration mechanism are attached to a single lapping machine. In the machining process, ultrasonic vibration enables the diamond slurry to smoothly pass through the microscopic holes of bamboo charcoal; the end of the bamboo charcoalis able to continue machining on the surface of the workpiece through the grasping force which exists in the microscopic holes. Under the polishing and machining parameters of ultrasonic-assisted vibration, with a diamond slurry concentration of 0.3%, the experimental results show a polishing time of 20 min, a loading of 25 N on the workpiece surface, a spindle speed of 1200 rpm, a vibration frequency of 30 kHz and the original surface roughness value of Ra 0.252 μm equals that of a mirror-like surface at Ra 0.017 μm. These research results prove that by using bamboo charcoal and ultrasonic-assisted vibration for polishing, a very good improvement can be achieved on the workpiece surface.

Conformational and vibrational analysis of 5-hydroxy 2-nitrobenzaldehyde by AB initio hartree-fock, density functional theory calculations

International Nuclear Information System (INIS)

Cinakli, S.; Sert, Y.; Boeyuekata, M.; Ucun, F.

2010-01-01

The vibrational spectra of benzaldehyde and its derivatives have been studied earlier. The substitution of a functional group changes the spectra markedly. Recent spectroscopic studies of the benzaldehyde and their derivatives have been motivated because the vibrational spectra are very useful for understanding of specific biological process and in the analysis of relatively complex systems. The optimized molecular structure, vibrational frequencies and corresponding vibrational assignments, the total energy calculations, relative energies, the mean vibrational deviations of the two planar O-cis and O-trans roomers of 5-Hydroxy 2-nitrobenzaldehydes have been calculated using ab initio Hartree Fock (HF) and Density Functional Theory (B3LYP) with 6-311++G(d,p) basis set. All computations have been performed on personal computer using the Gaussian 03 program package. The calculations were adapted to Cs symmetries of all the molecules. The O-trans rotomers with lower energy of all the molecules have been found as preferential rotomers in the ground state.

Anharmonic vibrational modes of chemisorbed H on the Rh(001) surface

International Nuclear Information System (INIS)

Hamann, D.R.; Feibelman, P.J.

1988-01-01

The potential for H atoms in the vicinity of the fourfold hollow chemisorption site on the Rh(001) surface at monolayer coverage is calculated using local-density-functional theory, and the linear-augmented-plane-wave method. The potential is found to contain important anharmonic components, one that couples parallel and perpendicular motion, and another producing azimuthal anisotropy. Variational solutions are found for the ground and low-lying excited states of H and D in this potential. The fundamental asymmetric- and symmetric-stretch H vibrational excitations are found to have energies of 67 and 92 meV. The latter agrees with recent experimental results, and higher-lying experimental modes are interpreted as mixed excitations. Comparisons are made with spring-constant models, calculated potentials for H on Ni and Pd(001), and theories of Bloch states for H on Ni

Surface-enhanced Raman spectroscopy bioanalytical, biomolecular and medical applications

CERN Document Server

Procházka, Marek

2016-01-01

This book gives an overview of recent developments in RS and SERS for sensing and biosensing considering also limitations, possibilities and prospects of this technique. Raman scattering (RS) is a widely used vibrational technique providing highly specific molecular spectral patterns. A severe limitation for the application of this spectroscopic technique lies in the low cross section of RS. Surface-enhanced Raman scattering (SERS) spectroscopy overcomes this problem by 6-11 orders of magnitude enhancement compared with the standard RS for molecules in the close vicinity of certain rough metal surfaces. Thus, SERS combines molecular fingerprint specificity with potential single-molecule sensitivity. Due to the recent development of new SERS-active substrates, labeling and derivatization chemistry as well as new instrumentations, SERS became a very promising tool for many varied applications, including bioanalytical studies and sensing. Both intrinsic and extrinsic SERS biosensing schemes have been employed to...

Surface-enhanced vibrational spectroscopy of B vitamins: what is the effect of SERS-active metals used?

Science.gov (United States)

Kokaislová, A; Matějka, P

2012-05-01

Surface-enhanced Raman scattering (SERS) spectroscopy and surface-enhanced infrared absorption (SEIRA) spectroscopy are analytical tools suitable for the detection of small amounts of various analytes adsorbed on metal surfaces. During recent years, these two spectroscopic methods have become increasingly important in the investigation of adsorption of biomolecules and pharmaceuticals on nanostructured metal surfaces. In this work, the adsorption of B-group vitamins pyridoxine, nicotinic acid, folic acid and riboflavin at electrochemically prepared gold and silver substrates was investigated using Fourier transform SERS spectroscopy at an excitation wavelength of 1,064 nm. Gold and silver substrates were prepared by cathodic reduction on massive platinum targets. In the case of gold substrates, oxidation-reduction cycles were applied to increase the enhancement factor of the gold surface. The SERS spectra of riboflavin, nicotinic acid, folic acid and pyridoxine adsorbed on silver substrates differ significantly from SERS spectra of these B-group vitamins adsorbed on gold substrates. The analysis of near-infrared-excited SERS spectra reveals that each of B-group vitamin investigated interacts with the gold surface via a different mechanism of adsorption to that with the silver surface. In the case of riboflavin adsorbed on silver substrate, the interpretation of surface-enhanced infrared absorption (SEIRA) spectra was also helpful in investigation of the adsorption mechanism.

Infrared spectroscopic measurement of skin hydration and sebum levels and comparison to corneometer and sebumeter

Science.gov (United States)

Ezerskaia, Anna; Pereira, S. F.; Urbach, H. P.; Varghese, Babu

2016-05-01

Skin health characterized by a system of water and lipids in Stratum Corneum provide protection from harmful external elements and prevent trans-epidermal water loss. Skin hydration (moisture) and sebum (skin surface lipids) are considered to be important factors in skin health; a right balance between these components is an indication of skin health and plays a central role in protecting and preserving skin integrity. In this manuscript we present an infrared spectroscopic method for simultaneous and quantitative measurement of skin hydration and sebum levels utilizing differential detection with three wavelengths 1720, 1750, and 1770 nm, corresponding to the lipid vibrational bands that lie "in between" the prominent water absorption bands. The skin sebum and hydration values on the forehead under natural conditions and its variations to external stimuli were measured using our experimental set-up. The experimental results obtained with the optical set-up show good correlation with the results obtained with the commercially available instruments Corneometer and Sebumeter.

Developing and understanding biofluid vibrational spectroscopy: a critical review.

Science.gov (United States)

Baker, Matthew J; Hussain, Shawn R; Lovergne, Lila; Untereiner, Valérie; Hughes, Caryn; Lukaszewski, Roman A; Thiéfin, Gérard; Sockalingum, Ganesh D

2016-04-07

Vibrational spectroscopy can provide rapid, label-free, and objective analysis for the clinical domain. Spectroscopic analysis of biofluids such as blood components (e.g. serum and plasma) and others in the proximity of the diseased tissue or cell (e.g. bile, urine, and sputum) offers non-invasive diagnostic/monitoring possibilities for future healthcare that are capable of rapid diagnosis of diseases via specific spectral markers or signatures. Biofluids offer an ideal diagnostic medium due to their ease and low cost of collection and daily use in clinical biology. Due to the low risk and invasiveness of their collection they are widely welcomed by patients as a diagnostic medium. This review underscores recent research within the field of biofluid spectroscopy and its use in myriad pathologies such as cancer and infectious diseases. It highlights current progresses, advents, and pitfalls within the field and discusses future spectroscopic clinical potentials for diagnostics. The requirements and issues surrounding clinical translation are also considered.

Surface characteristics of PLA and PLGA films

Energy Technology Data Exchange (ETDEWEB)

Paragkumar N, Thanki [Laboratoire de Chimie-Physique Macromoleculaire (LCPM), UMR CNRS-INPL 7568, Groupe ENSIC, 1 rue Grandville, B.P. 20451, 54001 Nancy Cedex (France); Edith, Dellacherie [Laboratoire de Chimie-Physique Macromoleculaire (LCPM), UMR CNRS-INPL 7568, Groupe ENSIC, 1 rue Grandville, B.P. 20451, 54001 Nancy Cedex (France); Six, Jean-Luc [Laboratoire de Chimie-Physique Macromoleculaire (LCPM), UMR CNRS-INPL 7568, Groupe ENSIC, 1 rue Grandville, B.P. 20451, 54001 Nancy Cedex (France)]. E-mail: Jean-Luc.Six@ensic.inpl-nancy.fr

2006-12-30

Surface segregation and restructuring in polylactides (poly(D,L-lactide) and poly(L-lactide)) and poly(D,L-lactide-co-glycolide) (PLGA) films of various thicknesses were investigated using both attenuated total reflection FTIR (ATR-FTIR) and contact angle relaxation measurements. In case of poly(D,L-lactide) (DLPLA), it was observed that the surface segregation and the surface restructuring of methyl side groups are influenced by the polymer film thickness. This result has been confirmed by X-ray photoelectron spectroscopy (XPS). In the same way, PLGA thick films were also characterized by an extensive surface segregation of methyl side groups. Finally, surface restructuring was investigated by dynamic contact angle measurements and it was observed when film surface comes into contact with water. In parallel, we also found that poly(L-lactide) (PLLA) thin and clear films with thickness {approx}15 {mu}m undergo conformational changes on the surface upon solvent treatment with certain solvents. The solvent treated surface of PLLA becomes hazy and milky white and its hydrophobicity increases compared to untreated surface. FTIR spectroscopic analysis indicated that polymer chains at the surface undergo certain conformational changes upon solvent treatment. These changes are identified as the restricted motions of C-O-C segments and more intense and specific vibrations of methyl side groups. During solvent treatment, the change in water contact angle and FTIR spectrum of PLLA is well correlated.

Prediction of surface roughness in turning of Ti-6Al-4V using cutting parameters, forces and tool vibration

Science.gov (United States)

Sahu, Neelesh Kumar; Andhare, Atul B.; Andhale, Sandip; Raju Abraham, Roja

2018-04-01

Present work deals with prediction of surface roughness using cutting parameters along with in-process measured cutting force and tool vibration (acceleration) during turning of Ti-6Al-4V with cubic boron nitride (CBN) inserts. Full factorial design is used for design of experiments using cutting speed, feed rate and depth of cut as design variables. Prediction model for surface roughness is developed using response surface methodology with cutting speed, feed rate, depth of cut, resultant cutting force and acceleration as control variables. Analysis of variance (ANOVA) is performed to find out significant terms in the model. Insignificant terms are removed after performing statistical test using backward elimination approach. Effect of each control variables on surface roughness is also studied. Correlation coefficient (R2 pred) of 99.4% shows that model correctly explains the experiment results and it behaves well even when adjustment is made in factors or new factors are added or eliminated. Validation of model is done with five fresh experiments and measured forces and acceleration values. Average absolute error between RSM model and experimental measured surface roughness is found to be 10.2%. Additionally, an artificial neural network model is also developed for prediction of surface roughness. The prediction results of modified regression model are compared with ANN. It is found that RSM model and ANN (average absolute error 7.5%) are predicting roughness with more than 90% accuracy. From the results obtained it is found that including cutting force and vibration for prediction of surface roughness gives better prediction than considering only cutting parameters. Also, ANN gives better prediction over RSM models.

Spectroscopic measurement of H(1S) and H2(v double-prime,J double-prime) in an H- ion source plasma

International Nuclear Information System (INIS)

Stutzin, G.C.

1990-08-01

Low pressure H 2 discharges have been used for some time as sources of H - ions. These discharges contain many different species of particles which interact with each other and with the walls of the discharge chamber. Models exist that predict the populations of the various species for given macroscopic discharge parameters. However, many of the cross sections and wall catalyzation coefficients are unknown or somewhat uncertain. Therefore, it is of interest to measure the populations of as many of these species as possible, in order to determine the validity of the models. These models predict that H - is created predominantly by the two-step process of vibrational excitation of hydrogen molecules followed by dissociative attachment of slow electrons to these vibrationally-excited hydrogen molecules. Many different collisional processes must be included in the models to explain the dependence of the various populations upon macroscopic parameters. This work presents results of spectroscopic measurements of the density and translational temperature of hydrogen atoms and of specific rotationally- and vibrationally-excited states of electronic ground-state H 2 , in a discharge optimized for H - production, as well as conventional measurements of the various charged species within the plasma. The spectroscopic measurements are performed directly by narrowband, single-photon absorption in the vacuum ultraviolet

Built-up edge investigation in vibration drilling of Al2024-T6.

Science.gov (United States)

Barani, A; Amini, S; Paktinat, H; Fadaei Tehrani, A

2014-07-01

Adding ultrasonic vibrations to drilling process results in an advanced hybrid machining process, entitled "vibration drilling". This study presents the design and fabrication of a vibration drilling tool by which both rotary and vibrating motions are applied to drill simultaneously. High frequency and low amplitude vibrations were generated by an ultrasonic transducer with frequency of 19.65 kHz. Ultrasonic transducer was controlled by a MPI ultrasonic generator with 3 kW power. The drilling tool and workpiece material were HSS two-flute twist drill and Al2024-T6, respectively. The aim of this study was investigating on the effect of ultrasonic vibrations on built-up edge, surface quality, chip morphology and wear mechanisms of drill edges. Therefore, these factors were studied in both vibration and ordinary drilling. Based on the achieved results, vibration drilling offers less built-up edge and better surface quality compared to ordinary drilling. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of molecular organization in pentacene thin films on SiO{sub 2} surface using infrared spectroscopy, spectroscopic ellipsometry, and atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Frątczak, E.Z., E-mail: ewelinazofia@gmail.com [Faculty of Physics and Applied Informatics, University of Łódź, 90-236 Łódź, Pomorska 149/153 (Poland); Uznański, P., E-mail: puznansk@cbmm.lodz.pl [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 90-363 Łódź, Sienkiewicza 112 (Poland); Moneta, M.E. [Faculty of Physics and Applied Informatics, University of Łódź, 90-236 Łódź, Pomorska 149/153 (Poland)

2015-07-29

Highlights: • Pentacene thin films of different thickness grown onto SiO{sub 2} substrates were studied. • Polarized IR GATR spectra were recorded and conclusions on pentacene orientation were deduced. • Optical anisotropic properties and morphology of pentacene films were analyzed. • Dielectric properties vary to some extent with the film thickness. - Abstract: Thin films of pentacene of 32 and 100 nm thickness obtained by organic molecular beam deposition (OMBD) in high vacuum conditions onto silicon/native silica (Si/SiO{sub 2}) and fused silica substrates were examined. Alignment, anisotropic optical properties and morphology were studied in ambient conditions using infrared (IR) transmission and polarized grazing angle attenuated total reflection (GATR) techniques, variable angle spectroscopic ellipsometry (VASE), UV–VIS absorption, and atomic force microscopy (AFM). For the first time dichroic GATR IR spectra were recorded for such thin films and conclusions on pentacene orientation were deduced on the basis of dichroic ratio of the IR-active vibrations. The symmetry assignment of the vibrational transitions is also discussed. The films exhibit continuous globular texture with uniaxial alignment of pentacene molecules and strongly anisotropic optical properties evidenced in the ellipsometric measurements. The results revealed that there are some quantitative differences in the orientation and in the dielectric properties between the two pentacene films of different thickness.

An experimental and theoretical study of molecular structure and vibrational spectra of 2-methylphenyl boronic acid by density functional theory calculations

Science.gov (United States)

Hiremath, Sudhir M.; Hiremath, C. S.; Khemalapure, S. S.; Patil, N. R.

2018-05-01

This paper reports the experimental and theoretical study on the structure and vibrations of 2-Methylphenyl boronic acid (2MPBA). The different spectroscopic techniques such as FT-IR (4000-400 cm-1) and FT-Raman (4000-50 cm-1) of the title molecule in the solid phase were recorded. The geometry of the molecule was fully optimized using density functional theory (DFT) (B3LYP) with 6-311++G(d, p) basis set calculations. The vibrational wavenumbers were also corrected with scale factor to take better results for the calculated data. Vibrational spectra were calculated and fundamental vibrations were assigned on the basis of the potential energy distribution (PED) of the vibrational modes obtained from VEDA 4 program. The calculated wavenumbers showed the best agreement with the experimental results. Whereas, it is observed that, the theoretical frequencies are more than the experimental one for O-H stretching vibration modes of the title molecule.

Spectroscopic studies on novel donor-acceptor and low band-gap polymeric semiconductors

International Nuclear Information System (INIS)

Cravino, A.

2002-11-01

Novel low band-gap conjugated polymeric semiconductors as well as conjugated electron donor chains carrying electron acceptor substituents were electrochemically prepared and investigated by means of different spectroscopic techniques. Using in situ FTIR and ESR spectroelectrochemistry, the spectroscopic features of injected positive charges are found to be different as opposed to the negative charge carriers on the same conjugated polymer. These results, for which the theoretical models so far developed do not account, demonstrate the different structure and delocalization of charge carriers with opposite signs. In addition, vibrational spectroscopy results proof the enhanced 'quinoid' character of low band-gap conjugated chains. Excited state spectroscopy was applied to study photoexcitations in conjugated polymers carrying tetracyanoanthraquinone type or fullerene moieties. This novel class of materials, hereafter called double-cable polymers, was found promising as alternative to the conjugated polymer:fullerene mixtures currently used for the preparation of 'bulk-heterojunction' polymeric solar cells. (author)

Evaluation Of Vibration-Monitoring Gear-Diagnostic System

Science.gov (United States)

Townsend, Dennis P.; Zakrajsek, James J.

1995-01-01

Report describes experimental evaluation of commercial electronic system designed to monitor vibration signal from accelerometer on gear-box to detect vibrations indicative of damage to gears. System includes signal-conditioning subsystem and personal computer in which analog-to-digital converter installed. Results show system fairly effective in detecting surface fatigue pits on spur-gear teeth.

Rotational and High-resolution Infrared Spectrum of HC3N: Global Ro-vibrational Analysis and Improved Line Catalog for Astrophysical Observations

Science.gov (United States)

Bizzocchi, Luca; Tamassia, Filippo; Laas, Jacob; Giuliano, Barbara M.; Degli Esposti, Claudio; Dore, Luca; Melosso, Mattia; Canè, Elisabetta; Pietropolli Charmet, Andrea; Müller, Holger S. P.; Spahn, Holger; Belloche, Arnaud; Caselli, Paola; Menten, Karl M.; Garrod, Robin T.

2017-11-01

HC3N is a ubiquitous molecule in interstellar environments, from external galaxies to Galactic interstellar clouds, star-forming regions, and planetary atmospheres. Observations of its rotational and vibrational transitions provide important information on the physical and chemical structures of the above environments. We present the most complete global analysis of the spectroscopic data of HC3N. We recorded the high-resolution infrared spectrum from 450 to 1350 cm-1, a region dominated by the intense {ν }5 and {ν }6 fundamental bands, located at 660 and 500 cm-1, respectively, and their associated hot bands. Pure rotational transitions in the ground and vibrationally excited states were recorded in the millimeter and submillimeter regions in order to extend the frequency range so far considered in previous investigations. All of the transitions from the literature and from this work involving energy levels lower than 1000 cm-1 were fitted together to an effective Hamiltonian. Because of the presence of various anharmonic resonances, the Hamiltonian includes a number of interaction constants, in addition to the conventional rotational and vibrational l-type resonance terms. The data set contains about 3400 ro-vibrational lines of 13 bands and some 1500 pure rotational lines belonging to 12 vibrational states. More than 120 spectroscopic constants were determined directly from the fit, without any assumption deduced from theoretical calculations or comparisons with similar molecules. An extensive list of highly accurate rest frequencies was produced to assist astronomical searches and data interpretation. These improved data enabled a refined analysis of the ALMA observations toward Sgr B2(N2).

Vibration welding system with thin film sensor

Science.gov (United States)

Cai, Wayne W; Abell, Jeffrey A; Li, Xiaochun; Choi, Hongseok; Zhao, Jingzhou

2014-03-18

A vibration welding system includes an anvil, a welding horn, a thin film sensor, and a process controller. The anvil and horn include working surfaces that contact a work piece during the welding process. The sensor measures a control value at the working surface. The measured control value is transmitted to the controller, which controls the system in part using the measured control value. The thin film sensor may include a plurality of thermopiles and thermocouples which collectively measure temperature and heat flux at the working surface. A method includes providing a welder device with a slot adjacent to a working surface of the welder device, inserting the thin film sensor into the slot, and using the sensor to measure a control value at the working surface. A process controller then controls the vibration welding system in part using the measured control value.

Theoretical rotation-vibration spectrum of thioformaldehyde

International Nuclear Information System (INIS)

Yachmenev, Andrey; Polyak, Iakov; Thiel, Walter

2013-01-01

We present a variational calculation of the first comprehensive T = 300 K rovibrational line list for thioformaldehyde, H 2 CS. It covers 41 809 rovibrational levels for states up to J max = 30 with vibrational band origins up to 5000 cm −1 and provides the energies and line intensities for 547 926 transitions from the ground vibrational state to these levels. It is based on our previously reported accurate ab initio potential energy surface and a newly calculated ab initio dipole moment surface. Minor empirical adjustments are made to the ab initio equilibrium geometry to reduce systematic errors in the predicted intra-band rotational energy levels. The rovibrational energy levels and transition intensities are computed variationally by using the methods implemented in the computer program TROVE. Transition wavelengths and intensities are found to be in excellent agreement with the available experimental data. The present calculations correctly reproduce the observed resonance effects, such as intensity borrowing, thus reflecting the high accuracy of the underlying ab initio surfaces. We report a detailed analysis of several vibrational bands, especially those complicated by strong Coriolis coupling, to facilitate future laboratory assignments

Theoretical rotation-vibration spectrum of thioformaldehyde

Science.gov (United States)

Yachmenev, Andrey; Polyak, Iakov; Thiel, Walter

2013-11-01

We present a variational calculation of the first comprehensive T = 300 K rovibrational line list for thioformaldehyde, H2CS. It covers 41 809 rovibrational levels for states up to Jmax = 30 with vibrational band origins up to 5000 cm-1 and provides the energies and line intensities for 547 926 transitions from the ground vibrational state to these levels. It is based on our previously reported accurate ab initio potential energy surface and a newly calculated ab initio dipole moment surface. Minor empirical adjustments are made to the ab initio equilibrium geometry to reduce systematic errors in the predicted intra-band rotational energy levels. The rovibrational energy levels and transition intensities are computed variationally by using the methods implemented in the computer program TROVE. Transition wavelengths and intensities are found to be in excellent agreement with the available experimental data. The present calculations correctly reproduce the observed resonance effects, such as intensity borrowing, thus reflecting the high accuracy of the underlying ab initio surfaces. We report a detailed analysis of several vibrational bands, especially those complicated by strong Coriolis coupling, to facilitate future laboratory assignments.

Theoretical rotation-vibration spectrum of thioformaldehyde

Energy Technology Data Exchange (ETDEWEB)

Yachmenev, Andrey [Department of Physics and Astronomy, University College London, London, WC1E 6BT (United Kingdom); Polyak, Iakov; Thiel, Walter [Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D–45470 Mülheim an der Ruhr (Germany)

2013-11-28

We present a variational calculation of the first comprehensive T = 300 K rovibrational line list for thioformaldehyde, H{sub 2}CS. It covers 41 809 rovibrational levels for states up to J{sub max} = 30 with vibrational band origins up to 5000 cm{sup −1} and provides the energies and line intensities for 547 926 transitions from the ground vibrational state to these levels. It is based on our previously reported accurate ab initio potential energy surface and a newly calculated ab initio dipole moment surface. Minor empirical adjustments are made to the ab initio equilibrium geometry to reduce systematic errors in the predicted intra-band rotational energy levels. The rovibrational energy levels and transition intensities are computed variationally by using the methods implemented in the computer program TROVE. Transition wavelengths and intensities are found to be in excellent agreement with the available experimental data. The present calculations correctly reproduce the observed resonance effects, such as intensity borrowing, thus reflecting the high accuracy of the underlying ab initio surfaces. We report a detailed analysis of several vibrational bands, especially those complicated by strong Coriolis coupling, to facilitate future laboratory assignments.

Spectroscopic studies of surface-gas interactions and catalyst restructuring at ambient pressure: mind the gap!

International Nuclear Information System (INIS)

Rupprechter, Guenther; Weilach, Christian

2008-01-01

Recent progress in the application of surface vibrational spectroscopy at ambient pressure allows us to monitor surface-gas interactions and heterogeneous catalytic reactions under conditions approaching those of technical catalysis. The surface specificity of photon-based methods such as polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and sum frequency generation (SFG) spectroscopy is utilized to monitor catalytically active surfaces while they function at high pressure and high temperature. Together with complementary information from high-pressure x-ray photoelectron spectroscopy (HP-XPS) and high-resolution transmission electron microscopy (HRTEM), reaction mechanisms can be deduced on a molecular level. Well defined model catalysts, prepared under ultrahigh vacuum (UHV), are typically employed in such studies, including smooth and stepped single crystals, thin oxide films, and oxide-supported nanoparticles. A number of studies on unsupported and supported noble metal (Pd, Rh) catalysts are presented, focusing on the transformation of the catalysts from the 'as-prepared' to the 'active state'. This often involves pronounced alterations in catalyst structure and composition, for example the creation of surface carbon phases, surface oxides or surface alloys, as well as nanoparticle restructuring. The reactivity studies include CH 3 OH, CH 4 and CO oxidation with gas phase analysis by gas chromatography and mass spectrometry. Differing results between studies under ultrahigh vacuum and ambient pressure, and between studies on single crystals and supported nanoparticles, demonstrate the importance of 'minding the gap' between idealized and realistic conditions

Vibrational transition moments of CH4 from first principles

Science.gov (United States)

Yurchenko, Sergei N.; Tennyson, Jonathan; Barber, Robert J.; Thiel, Walter

2013-09-01

New nine-dimensional (9D), ab initio electric dipole moment surfaces (DMSs) of methane in its ground electronic state are presented. The DMSs are computed using an explicitly correlated coupled cluster CCSD(T)-F12 method in conjunction with an F12-optimized correlation consistent basis set of the TZ-family. A symmetrized molecular bond representation is used to parameterise these 9D DMSs in terms of sixth-order polynomials. Vibrational transition moments as well as band intensities for a large number of IR-active vibrational bands of 12CH4 are computed by vibrationally averaging the ab initio dipole moment components. The vibrational wavefunctions required for these averages are computed variationally using the program TROVE and a new ‘spectroscopic’ 12CH4 potential energy surface. The new DMSs will be used to produce a hot line list for 12CH4.

Far-infrared Spectroscopic Characterization of Anti-vinyl Alcohol

Science.gov (United States)

Bunn, Hayley; Soliday, Rebekah M.; Sumner, Isaiah; Raston, Paul L.

2017-09-01

We report a detailed analysis of the high-resolution far-infrared spectrum of anti-vinyl alcohol, which has been previously identified toward Sagittarius B2(N). The ν 15 OH torsional fundamental investigated here is more than 200 cm-1 removed from the next nearest vibration, making it practically unperturbed and ideal to help refine the ground state rotational constants that were previously determined from 25 microwave lines. We assigned 1335 lines within the ν 15 fundamental centered at 261.5512 cm-1, with J and K a ranges of 1-59 and 0-16, respectively. The microwave and far-infrared line positions were fit with Watson-type A- and S-reduced Hamiltonians, with the inclusion of quartic and select sextic distortion terms. This resulted in a significant refinement of the ground state constants, in addition to the determination of the {ν }15=1 state constants for the first time. The spectroscopic parameters are in good agreement with the results from anharmonic coupled-cluster calculations, and should be useful in searches for rotationally and/or vibrationally warm anti-vinyl alcohol in interstellar molecular clouds.

Vibrational excitation from heterogeneous catalysis

International Nuclear Information System (INIS)

Purvis, G.D. III; Redmon, M.J.; Woken, G. Jr.

1979-01-01

Classical trajectories have been used by numerous researchers to investigate the dynamics of exothermic chemical reactions (atom + diatom) with a view toward understanding what leads to vibrational excitation of the product molecule. Unlike these studies, the case where the reaction is catalyzed by a solid surface is considered. The trajectory studies indicate that there should be conditions under which considerable vibrational energy appears in the product molecules without being lost to the solid during the course of the reaction. 2 figures, 3 tables

Rotational Spectra in 29 Vibrationally Excited States of Interstellar Aminoacetonitrile

Energy Technology Data Exchange (ETDEWEB)

Kolesniková, L.; Alonso, E. R.; Mata, S.; Alonso, J. L. [Grupo de Espectroscopia Molecular (GEM), Edificio Quifima, Área de Química-Física, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Unidad Asociada CSIC, Universidad de Valladolid, E-47011 Valladolid (Spain)

2017-04-01

We report a detailed spectroscopic investigation of the interstellar aminoacetonitrile, a possible precursor molecule of glycine. Using a combination of Stark and frequency-modulation microwave and millimeter wave spectroscopies, we observed and analyzed the room-temperature rotational spectra of 29 excited states with energies up to 1000 cm{sup −1}. We also observed the {sup 13}C isotopologues in the ground vibrational state in natural abundance (1.1%). The extensive data set of more than 2000 new rotational transitions will support further identifications of aminoacetonitrile in the interstellar medium.

Detection of hidden stationary deformations of vibrating surfaces by use of time-averaged digital holographic interferometry.

Science.gov (United States)

Demoli, Nazif; Vukicevic, Dalibor

2004-10-15

A method of detecting displacements of a surface from its steady-state position to its equilibrium position while it is vibrating has been developed by use of time-average digital holographic interferometry. This method permits extraction of such a hidden deformation by creating two separated systems of interferogram fringes: one corresponding to a time-varying resonantly oscillating optical phase, the other to the stationary phase modification. A mathematical description of the method and illustrative results of experimental verification are presented.

Report on planning of input earthquake vibration for design of vibration controlling structure, in the Tokai Works, Power Reactor and Nuclear Fuel Development Corporation

International Nuclear Information System (INIS)

Uryu, Mitsuru; Shinohara, Takaharu; Terada, Shuji; Yamazaki, Toshihiko; Nakayama, Kazuhiko; Kondo, Toshinari; Hosoya, Hisashi

1997-05-01

When adopting a vibration controlling structure for a nuclear facility building, it is necessary to evaluate a little longer frequency vibration properly. Although various evaluation methods are proposed, there is no finished method. And, to the earthquake itself to investigate, some factors such as effect of surface wave, distant great earthquake, and so on must be considered, and further various evaluations and investigations are required. Here is reported on an evaluation method of the input earthquake vibration for vibration controlling design establishing on adoption of the vibration controlling structure using a vibration control device comprising of laminated rubber and lead damper for the buildings of reprocessing facility in Tokai Works. The input earthquake vibration for vibration controlling design shown in this report is to be adopted for a vibration controlling facility buildings in the Tokai Works. (G.K.)

Experimental and DFT studies on the vibrational spectra of 1H-indene-2-boronic acid

Science.gov (United States)

Alver, Özgur; Kaya, Mehmet Fatih

2014-11-01

Stable conformers and geometrical molecular structures of 1H-indene-2-boronic acid (I-2B(OH)2) were studied experimentally and theoretically using FT-IR and FT-Raman spectroscopic methods. FT-IR and FT-Raman spectra were recorded in the region of 4000-400 cm-1, and 3700-400 cm-1, respectively. The optimized geometric structures were searched by Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-31++G(d,p) basis set. Vibrational wavenumbers of I-2B(OH)2 were calculated using B3LYP density functional methods including 6-31++G(d,p) basis set. Experimental and theoretical results show that density functional B3LYP method gives satisfactory results for predicting vibrational wavenumbers except OH stretching modes which is probably due to increasing unharmonicity in the high wave number region and possible intra and inter molecular interaction at OH edges. To support the assigned vibrational wavenumbers, the potential energy distribution (PED) values were also calculated using VEDA 4 (Vibrational Energy Distribution Analysis) program.

Asymptotically-correct description of vibration-rotation spectrum of diatomic molecule with hydrogen iodide molecule as example

International Nuclear Information System (INIS)

Burenin, A.V.; Ryabikin, M.Yu.

1990-01-01

Asymptotically correct series of perturbation theory was constructed analytically to describe the vibration-rotational spectrum of diatomic molecule in Born-Oppenheimer approximation. The series was used for processing of precision experimental data on frequencies of absorption of hydrogen iodide molecule. Advantage of this approach over Dunham approach is shown. Isotope ratios for spectroscopic constants of asymptotically correct series are considered

Report of workshop on vibration related to fluid in atomic energy field. 7

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-12-31

Because of the nonlinearity of the equation that governs flow, sometimes vibration occurs in an unexpected system, and it causes trouble. This 7th workshop on vibration related to fluid in atomic energy field was held at Nuclear Engineering Research Laboratory of University of Tokyo on August 25 and 26, 1997. Two themes were ``Vibration of liquid surface by flow`` and ``Numerical analysis of coupled vibration of fluid-structures``. The former is related to the problem in the development of a demonstration FBR, and the latter is related to the numerical analysis technology such as the handling of boundary conditions and the method of taking position, moving velocity and acceleration into account. This workshop aims at thoroughly discussing a small number of themes, and deepening the understanding. In this report, the summaries of 17 papers are collected, of which the titles are as follows. Liquid surface self-exciting vibration by flow, vibration of upper plenum liquid surface of fast reactor, stability analysis of multiple liquid surfaces, flow instability phenomena of multi-loop system, sloshing in a vessel in which fluid flows, the mechanism of occurrence of self-exciting sloshing in a vessel elucidated by numerical analysis, numerical analysis of manometer vibration excited by flow, numerical analysis of flutter phenomena of aircraft, numerical analysis of aerodynamic elastic problem, mechanism of in-line excitation, numerical analysis of hydrodynamic elastic vibration of tube nest and so on. (K.I.)

Effect of angle on flow-induced vibrations of pinniped vibrissae.

Directory of Open Access Journals (Sweden)

Christin T Murphy

Full Text Available Two types of vibrissal surface structures, undulated and smooth, exist among pinnipeds. Most Phocidae have vibrissae with undulated surfaces, while Otariidae, Odobenidae, and a few phocid species possess vibrissae with smooth surfaces. Variations in cross-sectional profile and orientation of the vibrissae also exist between pinniped species. These factors may influence the way that the vibrissae behave when exposed to water flow. This study investigated the effect that vibrissal surface structure and orientation have on flow-induced vibrations of pinniped vibrissae. Laser vibrometry was used to record vibrations along the whisker shaft from the undulated vibrissae of harbor seals (Phoca vitulina and northern elephant seals (Mirounga angustirostris and the smooth vibrissae of California sea lions (Zalophus californianus. Vibrations along the whisker shaft were measured in a flume tank, at three orientations (0°, 45°, 90° to the water flow. The results show that vibration frequency and velocity ranges were similar for both undulated and smooth vibrissae. Angle of orientation, rather than surface structure, had the greatest effect on flow-induced vibrations. Vibration velocity was up to 60 times higher when the wide, flat aspect of the whisker faced into the flow (90°, compared to when the thin edge faced into the flow (0°. Vibration frequency was also dependent on angle of orientation. Peak frequencies were measured up to 270 Hz and were highest at the 0° orientation for all whiskers. Furthermore, CT scanning was used to quantify the three-dimensional structure of pinniped vibrissae that may influence flow interactions. The CT data provide evidence that all vibrissae are flattened in cross-section to some extent and that differences exist in the orientation of this profile with respect to the major curvature of the hair shaft. These data support the hypothesis that a compressed cross-sectional profile may play a key role in reducing self

Mid-infrared spectroscopic investigation

International Nuclear Information System (INIS)

Walter, L.; Vergo, N.; Salisbury, J.W.

1987-01-01

Mid-infrared spectroscopic research efforts are discussed. The development of a new instrumentation to permit advanced measurements in the mid-infrared region of the spectrum, the development of a special library of well-characterized mineral and rock specimens for interpretation of remote sensing data, and cooperative measurements of the spectral signatures of analogues of materials that may be present on the surfaces of asteroids, planets or their Moons are discussed

Effects of vibration frequency on vibration-assisted nano-scratch process of mono-crystalline copper via molecular dynamics simulation

Directory of Open Access Journals (Sweden)

Bo Zhu

2016-03-01

Full Text Available It has always been a critical issue to understand the material removal behavior of Vibration-Assisted Machining (VAM, especially on atomic level. To find out the effects of vibration frequency on material removal response, a three-dimensional molecular dynamics (MD model has been established in this research to investigate the effects of scratched groove, crystal defects on the surface quality, comparing with the Von Mises shear strain and tangential force in simulations during nano-scratching process. Comparisons are made among the results of simulations from different vibration frequency with the same scratching feed, depth, amplitude and crystal orientation. Copper potential in this simulation is Embedded-Atom Method (EAM potential. Interaction between copper and carbon atoms is Morse potential. Simulational results show that higher frequency can make groove smoother. Simulation with high frequency creates more dislocations to improve the machinability of copper specimen. The changing frequency does not have evident effects on Von Mises shear strain. Higher frequency can decrease the tangential force to reduce the consumption of cutting energy and tool wear. In conclusion, higher vibration frequency in VAM on mono-crystalline copper has positive effects on surface finish, machinablility and tool wear reduction.

Effects of vibration frequency on vibration-assisted nano-scratch process of mono-crystalline copper via molecular dynamics simulation

Energy Technology Data Exchange (ETDEWEB)

Zhu, Bo; Zhao, Hongwei, E-mail: hwzhao@jlu.edu.cn, E-mail: khl69@163.com; Zhao, Dan; Zhang, Peng; Yang, Yihan; Han, Lei [School of Mechanical Science and Engineering, Jilin University, 5988 Renmin Street, Changchun, Jilin 130025 (China); Kui, Hailin, E-mail: hwzhao@jlu.edu.cn, E-mail: khl69@163.com [School of Transportation, Jilin University, 5988 Renmin Street, Changchun, Jilin 130025 (China)

2016-03-15

It has always been a critical issue to understand the material removal behavior of Vibration-Assisted Machining (VAM), especially on atomic level. To find out the effects of vibration frequency on material removal response, a three-dimensional molecular dynamics (MD) model has been established in this research to investigate the effects of scratched groove, crystal defects on the surface quality, comparing with the Von Mises shear strain and tangential force in simulations during nano-scratching process. Comparisons are made among the results of simulations from different vibration frequency with the same scratching feed, depth, amplitude and crystal orientation. Copper potential in this simulation is Embedded-Atom Method (EAM) potential. Interaction between copper and carbon atoms is Morse potential. Simulational results show that higher frequency can make groove smoother. Simulation with high frequency creates more dislocations to improve the machinability of copper specimen. The changing frequency does not have evident effects on Von Mises shear strain. Higher frequency can decrease the tangential force to reduce the consumption of cutting energy and tool wear. In conclusion, higher vibration frequency in VAM on mono-crystalline copper has positive effects on surface finish, machinablility and tool wear reduction.

Investigation on spectroscopic parameters and molecular constants of BeS(X1Σ+) using MRCI theory

International Nuclear Information System (INIS)

Liu Hui; Xing Wei; Shi Deheng; Sun Jinfeng

2012-01-01

The potential energy curve (PEC) of BeS(X 1 Σ + ) molecule has been studied using MRCI approach with Davidson modification in conjunction with the cc-pV5Z basis set. Effects on the PECs by the core-valence correlation corrections and relativistic effects have been taken into account. The way to consider the relativistic effects is to use the second-order Douglas-Kroll Hamiltonian approximation. With the PEC including the core-valence correlation corrections and relativistic effects, the spectroscopic parameters of BeS(X 1 Σ + ) have been determined. These parameters are compared in detail with those of previous studies reported in the literature, and excellent agreement has been found between the available experimental data and the present ones. With the PEC corrected, the first 40 vibrational states for the non-rotating BeS are computed, and the vibrational level, inertial rotation and centrifugal distortion constants for each vibrational state are predicted. (authors)

Investigation into high-frequency-vibration assisted micro-blanking of pure copper foils

Directory of Open Access Journals (Sweden)

Wang Chunju

2015-01-01

Full Text Available The difficulties encountered during the manufacture of microparts are often associated with size effects relating to material, process and tooling. Utilizing acoustoplastic softening, achieved through a high-frequency vibration assisted micro-blanking process, was introduced to improve the surface finish in micro-blanking. A frequency of 1.0 kHz was chosen to activate the longitudinal vibration mode of the horn tip, using a piezoelectric actuator. A square hole with dimensions of 0.5 mm × 0.5 mm was made, successfully, from a commercial rolled T2 copper foil with 100 μm in thickness. It was found that the maximum blanking force could be reduced by 5% through utilizing the high-frequency vibration. Proportion of the smooth, burnished area in the cut cross-section increases with an increase of the plasticity to fracture, under the high-frequency vibration, which suggests that the vibration introduced is helpful for inhibiting evolution of the crack due to its acoustoplastic softening effect. During blanking, roughness of the burnished surface could be reduced by increasing the vibration amplitude of the punch, which played a role as surface polishing. The results obtained suggest that the high-frequency vibration can be adopted in micro-blanking in order to improve quality of the microparts.

Critical insights into nuclear collectivity from complementary nuclear spectroscopic methods

Science.gov (United States)

Garrett, P. E.; Wood, J. L.; Yates, S. W.

2018-06-01

Low-energy collectivity of nuclei has been, and is being, characterized in a critical manner using data from a variety of spectroscopic methods, including Coulomb excitation, β decay, inelastic scattering of charged and uncharged particles, transfer reactions, etc. In addition to level energies and spins, transition multipolarities and intensities, lifetimes, and nuclear moments are available. The totality of information from these probes must be considered in achieving an accurate vision of the excitations in nuclei and determining the applicability of nuclear models. From these data, major changes in our view of low-energy collectivity in nuclei have emerged; most notable is the demise of the long-held view of low-energy quadrupole collectivity near closed shells as due to vibrations about a spherical equilibrium shape. In this contribution, we focus on the basic predictions of the spherical harmonic vibrator limit of the Bohr Hamiltonian. Properties such as B(E2) values, quadrupole moments, E0 strengths, etc are outlined. Using the predicted properties as a guide, evidence is cited for and against the existence of vibrational states, and especially multi-phonon states, in nuclei that are, or historically were considered to be, spherical or have a nearly spherical shape in their ground state. It is found that very few of the nuclei that were identified in the last major survey seeking nearly spherical harmonic vibrators satisfy the more stringent guidelines presented herein. Details of these fundamental shifts in our view of low-energy collectivity in nuclei are presented.

Spectroscopic studies of organometallic compounds on single crystal metal surfaces: Surface acetylides of silver (110)

Science.gov (United States)

Madix, Robert J.

indicated that the carbon atoms in the surface acetylide became inequivalent. Heating to 300 K produced a single peak at 282.8 eV which reverted to 283.4 when heated above 550 K; the carbon atoms became chemically equivalent. This latter state could be removed completely by O 2 to form CO 2(3). The XPS results showed quantitative conversion of all surface carbon from each state observed. Conclusive evidence regarding the identity of these states was obtained with titration experiments with deuterated acetic acid. CH 3COOD was adsorbed on top of the acetylenic residues at 150 K and heated to note the isotopes of acetylene that desorbed. The 275 K acetylene desorption peak, which showed inequivalent carbon atoms, was titrated by CH 3COOD to form C 2HD, indicating C 2H as the stable surface species. The species formed above 300 K, which showed equivalent carbon atoms in XPS, titrated to form C 2D 2, indicating a C 2 surface species. In each case the formulation of surface acetate was quantitative. The structure of these species was probed further with high resolution electron energy loss spectroscopy. The weakly chemisorbed molecular state exhibited vibrational losses at 300, 700 and 3270 cm -1, characteristics of an acetylene-surface stretching motion, a C-C-H bend and the C-H stretch respectively. No C-C stretch was observed, indicating that the molecule lay parallel to the plane of the surface. For adsorbed C 2H, bands were observed at 300, 690 and 3250cm -1. The high C-H stretching frequency indicated that the C-C bound order was near three. The absence of a C-C stretch in the spectrum was somewhat surprising, but was explained by a σ-π bonded complex in which the -C=CH species was flattened toward the surface by an interaction of an Ag atom with the π system of the acetylide.

Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

Science.gov (United States)

Marinov, Daniil; Guerra, Vasco; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine

2013-10-01

A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1-5 Torr and discharge currents ˜40-120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O_3^{*} , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O_3^{*} is strongly coupled with those of atomic oxygen and O2(a 1Δg) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established.

Ozone kinetics in low-pressure discharges: vibrationally excited ozone and molecule formation on surfaces

International Nuclear Information System (INIS)

Marinov, Daniil; Guaitella, Olivier; Booth, Jean-Paul; Rousseau, Antoine; Guerra, Vasco

2013-01-01

A combined experimental and modeling investigation of the ozone kinetics in the afterglow of pulsed direct current discharges in oxygen is carried out. The discharge is generated in a cylindrical silica tube of radius 1 cm, with short pulse durations between 0.5 and 2 ms, pressures in the range 1–5 Torr and discharge currents ∼40–120 mA. Time-resolved absolute concentrations of ground-state atoms and ozone molecules were measured simultaneously in situ, by two-photon absorption laser-induced fluorescence and ultraviolet absorption, respectively. The experiments were complemented by a self-consistent model developed to interpret the results and, in particular, to evaluate the roles of vibrationally excited ozone and of ozone formation on surfaces. It is found that vibrationally excited ozone, O 3 * , plays an important role in the ozone kinetics, leading to a decrease in the ozone concentration and an increase in its formation time. In turn, the kinetics of O 3 * is strongly coupled with those of atomic oxygen and O 2 (a 1 Δ g ) metastables. Ozone formation at the wall does not contribute significantly to the total ozone production under the present conditions. Upper limits for the effective heterogeneous recombination probability of O atoms into ozone are established. (paper)

Upgrading accuracy of designed seismic vibration on concept of the land conditions

International Nuclear Information System (INIS)

Tamura, Keichi; Kaneko, Masahiro; Honda, Toshiki; Chiba, Hikaru

1998-01-01

In this study, some investigations on design procedure of designed seismic vibration were conducted on concept of amplification of the seismic vibration and nonlinearity of the system at the place largely changing topographic and land conditions. In this fiscal year, after collecting and arranging the topographic and land conditions at settling place of the nuclear facilities and their circumferences, some investigations on effect of the seismic vibration amplified at surface layer of grounds on behavior of nonlinear system as well as arrangement of relationship between the topographic and land conditions and seismic vibration amplifying properties at the surface layer of grounds were conducted. (G.K.)

Vibrational relaxation and energy transfer of matrix isolated HCl and DCl

Energy Technology Data Exchange (ETDEWEB)

Wiesenfeld, J.M.

1977-12-01

Vibrational kinetic and spectroscopic studies have been performed on matrix-isolated HCl and DCl between 9 and 20 K. Vibrational relaxation rates for v = 2 and v = 1 were measured by a tunable infrared laser-induced, time-resolved fluorescence technique. In an Ar matrix, vibrational decay times are faster than radiative and it is found that HCl relaxes about 35 times more rapidly than CCl, in spite of the fact that HCl must transfer more energy to the lattice than DCl. This result is explained by postulating that the rate-determining step for vibrational relaxation produces a highly rotationally excited guest in a V yield R step; rotational relaxation into lattice phonons follows rapidly. HCl v = 1, but not v = 2, excitation rapidly diffuses through the sample by a resonant dipole-dipole vibrational energy transfer process. Molecular complexes, and in particular the HCl dimer, relax too rapidly for direct observation, less than or approximately 1 ..mu..s, and act as energy sinks in the energy diffusion process. The temperature dependence for all these processes is weak--less than a factor of two between 9 and 20 K. Vibrational relaxation of HCl in N/sub 2/ and O/sub 2/ matrices is unobservable, presumably due to rapid V yield V transfer to the host. A V yield R binary collision model for relaxation in solids is successful in explaining the HCl(DCl)/Ar results as well as results of other experimenters. The model considers relaxation to be the result of ''collisions'' due to molecular motion in quantized lattice normal modes--gas phase potential parameters can fit the matrix kinetic data.

Vibrational relaxation and energy transfer of matrix isolated HCl and DCl

International Nuclear Information System (INIS)

Wiesenfeld, J.M.

1977-12-01

Vibrational kinetic and spectroscopic studies have been performed on matrix-isolated HCl and DCl between 9 and 20 K. Vibrational relaxation rates for v = 2 and v = 1 were measured by a tunable infrared laser-induced, time-resolved fluorescence technique. In an Ar matrix, vibrational decay times are faster than radiative and it is found that HCl relaxes about 35 times more rapidly than CCl, in spite of the fact that HCl must transfer more energy to the lattice than DCl. This result is explained by postulating that the rate-determining step for vibrational relaxation produces a highly rotationally excited guest in a V yield R step; rotational relaxation into lattice phonons follows rapidly. HCl v = 1, but not v = 2, excitation rapidly diffuses through the sample by a resonant dipole-dipole vibrational energy transfer process. Molecular complexes, and in particular the HCl dimer, relax too rapidly for direct observation, less than or approximately 1 μs, and act as energy sinks in the energy diffusion process. The temperature dependence for all these processes is weak--less than a factor of two between 9 and 20 K. Vibrational relaxation of HCl in N 2 and O 2 matrices is unobservable, presumably due to rapid V yield V transfer to the host. A V yield R binary collision model for relaxation in solids is successful in explaining the HCl(DCl)/Ar results as well as results of other experimenters. The model considers relaxation to be the result of ''collisions'' due to molecular motion in quantized lattice normal modes--gas phase potential parameters can fit the matrix kinetic data

Optical properties and surface characterization of pulsed laser-deposited Cu2ZnSnS4 by spectroscopic ellipsometry

International Nuclear Information System (INIS)

Crovetto, Andrea; Cazzaniga, Andrea; Ettlinger, Rebecca B.; Schou, Jørgen; Hansen, Ole

2015-01-01

Cu 2 ZnSnS 4 films prepared by pulsed laser deposition at different temperatures are characterized by spectroscopic ellipsometry. The focus is on confirming results from direct measurement techniques, by finding appropriate models of the surface overlayer for data fitting, and extracting the dielectric function of the films. It is found that the surface overlayer changes with film thickness and deposition temperature. Adopting different ellipsometry measurements and modeling strategies for each film, dielectric functions are extracted and compared. As the deposition temperature is increased, the dielectric functions exhibit additional critical points related to optical transitions in the material other than absorption across the fundamental band gap. In the case of a thin film < 200 nm thick, surface features observed by scanning electron microscopy and atomic force microscopy are accurately reproduced by ellipsometry data fitting. - Highlights: • Inhomogeneous Cu 2 ZnSnS 4 films are prepared by pulsed laser deposition. • The film surface includes secondary phases and topographic structures. • We model a film surface layer that fits ellipsometry data. • Ellipsometry data fits confirm results from direct measurement techniques. • We obtain the dielectric function of inhomogeneous Cu 2 ZnSnS 4 films

Experimental Investigation of Ultrasonic Vibration Assisted Turning of 304 Austenitic Stainless Steel

Directory of Open Access Journals (Sweden)

Ping Zou

2015-01-01

vibration method is employed to scheme out a machining system of ultrasonic vibration assisted turning (MS-UAT. The experiments for turning the workpiece of ASS 304 are conducted with and without ultrasonic vibration using the designed MS-UAT, and then the 3D morphology evaluation parameters Sa and Sq are applied to characterize and analyse the machined surface. The experimental results obtained demonstrate that the process parameters in UAT of ASS 304 have obvious effect on the 3D surface topography and surface roughness of machined workpiece, and the appropriate choice of various process parameters, including ultrasonic amplitude, feed rate, depth of cut, and cutting speed, can enhance the machined surface quality efficiently to make the machining effect of UAT much better than that of CT.

Book Review: Reiner Salzer and Heinz W. Siesler (Eds.): Infrared and Raman spectroscopic imaging, 2nd ed

International Nuclear Information System (INIS)

Moore, David Steven

2015-01-01

This second edition of 'Infrared and Raman Spectroscopic Imaging' propels practitioners in that wide-ranging field, as well as other readers, to the current state of the art in a well-produced and full-color, completely revised and updated, volume. This new edition chronicles the expanded application of vibrational spectroscopic imaging from yesterday's time-consuming point-by-point buildup of a hyperspectral image cube, through the improvements afforded by the addition of focal plane arrays and line scan imaging, to methods applicable beyond the diffraction limit, instructs the reader on the improved instrumentation and image and data analysis methods, and expounds on their application to fundamental biomedical knowledge, food and agricultural surveys, materials science, process and quality control, and many others

Mechanism of bubble detachment from vibrating walls

Energy Technology Data Exchange (ETDEWEB)

Kim, Dongjun; Park, Jun Kwon, E-mail: junkeun@postech.ac.kr; Kang, Kwan Hyoung [Department of Mechanical Engineering, Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Pohang 790-784 (Korea, Republic of); Kang, In Seok [Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH), San 31, Hyoja-dong, Pohang 790-784 (Korea, Republic of)

2013-11-15

We discovered a previously unobserved mechanism by which air bubbles detach from vibrating walls in glasses containing water. Chaotic oscillation and subsequent water jets appeared when a wall vibrated at greater than a critical level. Wave forms were developed at water-air interface of the bubble by the wall vibration, and water jets were formed when sufficiently grown wave-curvatures were collapsing. Droplets were pinched off from the tip of jets and fell to the surface of the glass. When the solid-air interface at the bubble-wall attachment point was completely covered with water, the bubble detached from the wall. The water jets were mainly generated by subharmonic waves and were generated most vigorously when the wall vibrated at the volume resonant frequency of the bubble. Bubbles of specific size can be removed by adjusting the frequency of the wall's vibration.

Surface roughness estimation of MBE grown CdTe/GaAs(211)B by ex-situ spectroscopic ellipsometry

Energy Technology Data Exchange (ETDEWEB)

Karakaya, Merve, E-mail: mervegunnar@iyte.edu.tr [Department of Material Science and Engineering, Izmir Institute of Technology, Izmir 35430 (Turkey); Bilgilisoy, Elif; Arı, Ozan; Selamet, Yusuf [Department of Physics, Izmir Institute of Technology, Izmir 35430 (Turkey)

2016-07-15

Spectroscopic ellipsometry (SE) ranging from 1.24 eV to 5.05 eV is used to obtain the film thickness and optical properties of high index (211) CdTe films. A three-layer optical model (oxide/CdTe/GaAs) was chosen for the ex-situ ellipsometric data analysis. Surface roughness cannot be determined by the optical model if oxide is included. We show that roughness can be accurately estimated, without any optical model, by utilizing the correlation between SE data (namely the imaginary part of the dielectric function, <ε{sub 2} > or phase angle, ψ) and atomic force microscopy (AFM) roughness. <ε{sub 2} > and ψ values at 3.31 eV, which corresponds to E{sub 1} critical transition energy of CdTe band structure, are chosen for the correlation since E{sub 1} gives higher resolution than the other critical transition energies. On the other hand, due to the anisotropic characteristic of (211) oriented CdTe surfaces, SE data (<ε{sub 2} > and ψ) shows varieties for different azimuthal angle measurements. For this reason, in order to estimate the surface roughness by considering these correlations, it is shown that SE measurements need to be taken at the same surface azimuthal angle. Estimating surface roughness in this manner is an accurate way to eliminate cumbersome surface roughness measurement by AFM.

Quantum chemical calculations and spectroscopic measurements of spectroscopic and thermodynamic properties of given uranyl complexes in aqueous solutions with possible environmental and industrial applications

Directory of Open Access Journals (Sweden)

Višňak Jakub

2016-01-01

Full Text Available A brief introduction into computational methodology and preliminary results for spectroscopic (excitation energies, vibrational frequencies in ground and excited electronic states and thermodynamic (stability constants, standard enthalpies and entropies of complexation reactions properties of some 1:1, 1:2 and 1:3 uranyl sulphato- and selenato- complexes in aqueos solutions will be given. The relativistic effects are included via Effective Core Potential (ECP, electron correlation via (TDDFT/B3LYP (dispersion interaction corrected and solvation is described via explicit inclusion of one hydration sphere beyond the coordinated water molecules. We acknowledge limits of this approximate description – more accurate calculations (ranging from semi-phenomenological two-component spin-orbit coupling up to four-component Dirac-Coulomb-Breit hamiltonian and Molecular Dynamics simulations are in preparation. The computational results are compared with the experimental results from Time-resolved Laser-induced Fluorescence Spectroscopy (TRLFS and UV-VIS spectroscopic studies (including our original experimental research on this topic. In case of the TRLFS and UV-VIS speciation studies, the problem of complex solution spectra decomposition into individual components is ill-conditioned and hints from theoretical chemistry could be very important. Qualitative agreement between our quantum chemical calculations of the spectroscopic properties and experimental data was achieved. Possible applications for geochemical modelling (e.g. safety studies of nuclear waste repositories, modelling of a future mining site and analytical chemical studies (including natural samples are discussed.

Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation.

Science.gov (United States)

Planes, G A; Rodríguez, J L; Miras, M C; García, G; Pastor, E; Barbero, C A

2010-09-21

Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO(2) are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO(2) during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO(2) by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed.

Researches Concerning to Minimize Vibrations when Processing Normal Lathe

Directory of Open Access Journals (Sweden)

Lenuța Cîndea

2015-09-01

Full Text Available In the cutting process, vibration is inevitable appearance, and in situations where the amplitude exceeds the limits of precision dimensional and shape of the surfaces generated vibrator phenomenon is detrimental.Field vibration is an issue of increasingly developed, so the futures will a better understanding of them and their use even in other sectors.The paper developed experimental measurement of vibrations at the lathe machining normal. The scheme described kinematical machine tool, cutting tool, cutting conditions, presenting experimental facility for measuring vibration occurring at turning. Experimental results have followed measurement of amplitude, which occurs during interior turning the knife without silencer incorporated. The tests were performed continuously for different speed, feed and depth of cut.

Analysis of nonlinear vibrations and stability of rotating asymmetrical nano-shafts incorporating surface energy effects

Science.gov (United States)

Ghodousi, Maryam; Shahgholi, Majid; Payganeh, Gholamhassan

2018-03-01

The objective of the present work is to investigate the nonlinear vibrations of the rotating asymmetrical nano-shafts by considering surface effect. In order to compute the surface stress tensor, the surface elasticity theory is used. The governing nonlinear equations of motion are obtained with the aid of variational approach. Bubnov-Galerkin is a very effective method for exploiting the reduced-order model of the equations of motion. The averaging method is employed to analyze the reduced-order model of the system. For this purpose, the well-known Van der Pol transformation in the complex form and angle-action transformation are utilized. The effect of surface stress on the forward and backward speeds, steady state responses of the system, fixed points, close orbits and stability of the solutions is examined. The preliminary results of the research show that the absolute values of forward and backward whirling speeds in the presence of surface effect with positive residual surface stress are higher than those of regarding the system without surface effect and in the presence of surface effect with negative residual surface stress. In addition, it is seen that the undamped rotating asymmetrical nano-shaft, for specified value of detuning parameter, in the absence or presence of surface effect has various number of stable and unstable periodic solutions. Besides, there is different number of separatrix (homoclinic orbit type). Furthermore, bifurcations, number of solutions and their stability for damped rotating asymmetrical nano-shaft are investigated. Also, the above results have been obtained for rotating symmetrical nano-shaft.

Communication: atomic force detection of single-molecule nonlinear optical vibrational spectroscopy.

Science.gov (United States)

Saurabh, Prasoon; Mukamel, Shaul

2014-04-28

Atomic Force Microscopy (AFM) allows for a highly sensitive detection of spectroscopic signals. This has been first demonstrated for NMR of a single molecule and recently extended to stimulated Raman in the optical regime. We theoretically investigate the use of optical forces to detect time and frequency domain nonlinear optical signals. We show that, with proper phase matching, the AFM-detected signals closely resemble coherent heterodyne-detected signals. Applications are made to AFM-detected and heterodyne-detected vibrational resonances in Coherent Anti-Stokes Raman Spectroscopy (χ((3))) and sum or difference frequency generation (χ((2))).

Enhancing forensic science with spectroscopic imaging

Science.gov (United States)

Ricci, Camilla; Kazarian, Sergei G.

2006-09-01

This presentation outlines the research we are developing in the area of Fourier Transform Infrared (FTIR) spectroscopic imaging with the focus on materials of forensic interest. FTIR spectroscopic imaging has recently emerged as a powerful tool for characterisation of heterogeneous materials. FTIR imaging relies on the ability of the military-developed infrared array detector to simultaneously measure spectra from thousands of different locations in a sample. Recently developed application of FTIR imaging using an ATR (Attenuated Total Reflection) mode has demonstrated the ability of this method to achieve spatial resolution beyond the diffraction limit of infrared light in air. Chemical visualisation with enhanced spatial resolution in micro-ATR mode broadens the range of materials studied with FTIR imaging with applications to pharmaceutical formulations or biological samples. Macro-ATR imaging has also been developed for chemical imaging analysis of large surface area samples and was applied to analyse the surface of human skin (e.g. finger), counterfeit tablets, textile materials (clothing), etc. This approach demonstrated the ability of this imaging method to detect trace materials attached to the surface of the skin. This may also prove as a valuable tool in detection of traces of explosives left or trapped on the surfaces of different materials. This FTIR imaging method is substantially superior to many of the other imaging methods due to inherent chemical specificity of infrared spectroscopy and fast acquisition times of this technique. Our preliminary data demonstrated that this methodology will provide the means to non-destructive detection method that could relate evidence to its source. This will be important in a wider crime prevention programme. In summary, intrinsic chemical specificity and enhanced visualising capability of FTIR spectroscopic imaging open a window of opportunities for counter-terrorism and crime-fighting, with applications ranging

Structural and spectroscopic characterisations of the surface oxide scales and inclusions present on edge-burst hot-rolled steel coils

International Nuclear Information System (INIS)

Chowdhury, Anirban; Iyyappan, Ramasamy; Majumdar, Dipanwita; Singha, Achintya

2014-01-01

Detailed structural and spectroscopic characterisations have been carried out on the inclusions and the surface oxides present on edge-burst hot-rolled steel coils. Surface scales were characterised through X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. Evidence of different types of regular and non-stoichiometric Fe-oxides was found on the cracked surface of the steel wire. Along with the surface scales inclusions with calcium aluminate and spinel was characterized using Raman spectroscopy. The usefulness of Raman spectroscopy has been explored in detail for the characterisation of these inclusions; especially when XRD information ceases to be a limiting tool. The samples collected from the clogged nozzle area were found to be of grossite (CaO·2Al 2 O 3 ) phase and this was also observed in the inclusions in the finished coils. It was found that this particular calcium aluminate phase has a detrimental effect on casting and final finished steel products. - Highlights: • First investigation and surface study report on edge-bursting issue of steel coils. • Detailed characterisations of the inclusions and surface oxide scales in steel. • Influence of a particular type of calcium aluminate phase on process chemistry

Surface-enhanced Raman scattering: a new optical probe in molecular biophysics and biomedicine

DEFF Research Database (Denmark)

Kneipp, J.; Wittig, B.; Bohr, Henrik

2010-01-01

Sensitive and detailed molecular structural information plays an increasing role in molecular biophysics and molecular medicine. Therefore, vibrational spectroscopic techniques, such as Raman scattering, which provide high structural information content are of growing interest in biophysical and ...

Spectroscopic and electric dipole properties of Sr+Ar and SrAr systems including high excited states

Science.gov (United States)

Hamdi, Rafika; Abdessalem, Kawther; Dardouri, Riadh; Al-Ghamdi, Attieh A.; Oujia, Brahim; Gadéa, Florent Xavier

2018-01-01

The spectroscopic properties of the fundamental and several excited states of Sr+Ar and SrAr, Van der Waals systems are investigated by employing an ab initio method in a pseudo-potential approach. The potential energy curves and the spectroscopic parameters are displayed for the 1-10 2Σ+, 1-6 2Π and 1-3 2Δ electronic states of the Sr+Ar molecule and for the 1-6 1Σ+, 1-4 3Σ+, 1-3 1,3Π and 1-3 1,3Δ states of the neutral molecule SrAr. In addition, from these curves, the vibrational levels and their energy spacing are deduced for Σ+, Π and Δ symmetries. The spectra of the permanent and transition dipole moments are studied for the 1,3Σ+ states of SrAr, which are considered to be two-electron systems and 2Σ+ states of the single electron Sr+Ar ion. The spectroscopic parameters obtained for each molecular system are compared with previous theoretical and experimental works. A significant correlation revealed the accuracy of our results.

Magnitude of Neck-Surface Vibration as an Estimate of Subglottal Pressure during Modulations of Vocal Effort and Intensity in Healthy Speakers

Science.gov (United States)

McKenna, Victoria S.; Llico, Andres F.; Mehta, Daryush D.; Perkell, Joseph S.; Stepp, Cara E.

2017-01-01

Purpose: This study examined the relationship between the magnitude of neck-surface vibration (NSV[subscript Mag]; transduced with an accelerometer) and intraoral estimates of subglottal pressure (P'[subscript sg]) during variations in vocal effort at 3 intensity levels. Method: Twelve vocally healthy adults produced strings of /p?/ syllables in 3…

Enhanced vibration diagnostics using vibration signature analysis

International Nuclear Information System (INIS)

Ahmed, S.; Shehzad, K.; Zahoor, Y.; Mahmood, A.; Bibi, A.

2001-01-01

Symptoms will appear in equipment, as well as in human beings. when 'suffering from sickness. Symptoms of abnormality in equipment are vibration, noise, deformation, temperature, pressure, electric current, crack, wearing, leakage etc. these are called modes of failure. If the mode of failure is vibration then the vibration signature analysis can be effectively used in order to diagnose the machinery problems. Much valuable information is contained within these vibration 'Spectra' or 'Signatures' but is only of use if the analyst can unlock its 'Secrets'. This paper documents a vibration problem in the motor of a centrifugal pump (Type ETA). It focuses mainly on the roll of modern vibration monitoring system in problem analysis. The problem experienced was the motor unstability and noise due to high vibration. Using enhanced vibration signature data, the problem was analyzed. which suggested that the rotor eccentricity was the cause of excessive noise and vibration in the motor. In conclusion, advanced electronic monitoring and diagnostic systems provide powerful information for machine's condition assessment and problem analysis. Appropriate interpretation and use of this information is important for accurate and effective vibration analysis. (author)

Molecular approach of uranyl/mineral surfaces: experimental approach

International Nuclear Information System (INIS)

Drot, R.

2009-01-01

The author reports an experimental approach in which different spectroscopic approaches are coupled (laser spectroscopy, X-ray absorption spectroscopy, vibrational spectroscopy) to investigate the mechanisms controlling actinide sorption processes by different substrates, in order to assess radioactive waste storage site safety. Different substrates have been considered: monocrystalline or powdered TiO 2 , montmorillonite, and gibbsite

Heterodyne Angle Deviation Interferometry in Vibration and Bubble Measurements

OpenAIRE

Ming-Hung Chiu; Jia-Ze Shen; Jian-Ming Huang

2016-01-01

We proposed heterodyne angle deviation interferometry (HADI) for angle deviation measurements. The phase shift of an angular sensor (which can be a metal film or a surface plasmon resonance (SPR) prism) is proportional to the deviation angle of the test beam. The method has been demonstrated in bubble and speaker’s vibration measurements in this paper. In the speaker’s vibration measurement, the voltage from the phase channel of a lock-in amplifier includes the vibration level and frequency. ...

DFT simulations and vibrational spectra of 2-amino-2-methyl-1,3-propanediol

Science.gov (United States)

Renuga Devi, T. S.; Sharmi kumar, J.; Ramkumaar, G. R.

2014-12-01

The FTIR and FT-Raman spectra of 2-amino-2-methyl-1,3-propanediol were recorded in the regions 4000-400 cm-1 and 4000-50 cm-1 respectively. The structural and spectroscopic data of the molecule in the ground state were calculated using Hartee-Fock and density functional method (B3LYP) with the augmented-correlation consistent-polarized valence double zeta (aug-cc-pVDZ) basis set. The most stable conformer was optimized and the structural and vibrational parameters were determined based on this. The complete assignments were performed on the basis of the Potential Energy Distribution (PED) of the vibrational modes, calculated using Vibrational Energy Distribution Analysis (VEDA) 4 program. With the observed FTIR and FT-Raman data, a complete vibrational assignment and analysis of the fundamental modes of the compound were carried out. Thermodynamic properties and Mulliken charges were calculated using both Hartee-Fock and density functional method using the aug-cc-pVDZ basis set and compared. The calculated HOMO-LUMO energy gap revealed that charge transfer occurs within the molecule. 1H and 13C NMR chemical shifts of the molecule were calculated using Gauge-Independent Atomic Orbital (GIAO) method and were compared with experimental results.

Antagonistic properties of a natural product-Bicuculline with the gamma-aminobutyric acid receptor: studied through electrostatic potential mapping, electronic and vibrational spectra using ab initio and density functional theory.

Science.gov (United States)

Srivastava, Anubha; Tandon, Poonam; Jain, Sudha; Asthana, B P

2011-12-15

(+)-Bicuculline (hereinafter referred to as bicuculline), a phthalide isoquinoline alkaloid is of current interest as an antagonist of gamma-aminobutyric acid (GABA). Its inhibitor properties have been studied through molecular electrostatic potential (MEP) mapping of this molecule and GABA receptor. The hot site on the potential surface of bicuculline, which is also isosteric with GABA receptor, has been used to interpret the inhibitor property. A systematic quantum chemical study of the possible conformations, their relative stabilities, FT-Raman, FT-IR and UV-vis spectroscopic analysis of bicuculline has been reported. The optimized geometries, wavenumber and intensity of the vibrational bands of all the conformers of bicuculline have been calculated using ab initio Hartree-Fock (HF) and density functional theory (DFT) employing B3LYP functional and 6-311G(d,p) basis set. Mulliken atomic charges, HOMO-LUMO gap ΔE, ionization potential, dipole moments and total energy have also been obtained for the optimized geometries of both the molecules. TD-DFT method is used to calculate the electronic absorption parameters in gas phase as well as in solvent environment using integral equation formalism-polarizable continuum model (IEF-PCM) employing 6-31G basis set and the results thus obtained are compared with the UV absorption spectra. The combination of experimental and calculated results provides an insight into the structural and vibrational spectroscopic properties of bicuculline. Copyright © 2011 Elsevier B.V. All rights reserved.

The spectroscopic study of building composites containing natural sorbents.

Science.gov (United States)

Król, M; Mozgawa, W

2011-08-15

This work presents the results of FT-IR spectroscopic studies of heavy metal cations (Ag(+), Pb(2+), Zn(2+), Cd(2+) and Cr(3+)) immobilization from aqueous solutions on natural sorbents. The sorption has been conducted on sodium forms of zeolite (clinoptilolite) and clay minerals (mixtures containing mainly montmorillonite and kaolinite) which have been separated from natural Polish deposit. In the next part of the work both sorbents were used to obtain new building composites. It was proven those heavy metal cations' sorption causes changes in IR spectra of the zeolite and clay minerals. These alterations are dependent on the way the cations were sorbed. In the case of zeolite, variations of the bands corresponding to the characteristic ring vibrations have been observed. These rings occur in pseudomolecular complexes 4-4-1 (built of alumino- and silicooxygen tetrahedra) which constitute the secondary building units (SBU) and form spatial framework of the zeolite. The most significant changes have been determined in the region of pseudolattice vibrations (650-700 cm(-1)). In the instance of clay minerals, changes in the spectra occur at two ranges: 1200-800 cm(-1)--the range of the bands assigned to asymmetric Si-O(Si,Al) and bending Al-OH vibrations and 3800-3000 cm(-1)--the range of the bands originating from OH(-) groups stretching vibrations. Next results indicate possibilities of applying the used natural sorbents for the obtainment of new building materials having favourable composition and valuable properties. The zeolite was used for obtaining autoclaved materials with an addition of CaO, and the clay minerals for ceramic sintered materials with an addition of quartz and clinoptilolite were produced. FT-IR studies were also conducted on the obtained materials. Copyright © 2010 Elsevier B.V. All rights reserved.

Methods of performing downhole operations using orbital vibrator energy sources

Science.gov (United States)

Cole, Jack H.; Weinberg, David M.; Wilson, Dennis R.

2004-02-17

Methods of performing down hole operations in a wellbore. A vibrational source is positioned within a tubular member such that an annulus is formed between the vibrational source and an interior surface of the tubular member. A fluid medium, such as high bulk modulus drilling mud, is disposed within the annulus. The vibrational source forms a fluid coupling with the tubular member through the fluid medium to transfer vibrational energy to the tubular member. The vibrational energy may be used, for example, to free a stuck tubular, consolidate a cement slurry and/or detect voids within a cement slurry prior to the curing thereof.

Measurement of rabbit eardrum vibration through stroboscopic digital holography

Energy Technology Data Exchange (ETDEWEB)

De Greef, Daniël; Dirckx, Joris J. J. [University of Antwerp, Laboratory of BioMedical Physics, Groenenborgerlaan 171, B-2020 Antwerp (Belgium)

2014-05-27

In this work, we present a setup for high-power single shot stroboscopic digital holography and demonstrate it in an application on rabbit eardrum vibration measurement. The setup is able to make full-field time-resolved measurements of vibrating surfaces with a precision in the nanometer range in a broad frequency range. The height displacement of the measured object is visualized over the entire surface as a function of time. Vibration magnitude and phase maps can be extracted from these data, the latter proving to be very useful to reveal phase delays across the surface. Such deviations from modal motion indicate energy losses due to internal damping, in contrast to purely elastic mechanics. This is of great interest in middle ear mechanics and finite element modelling. In our setup, short laser pulses are fired at selected instants within the surface vibration period and are recorded by a CCD camera. The timing of the pulses and the exposure of the camera are synchronized to the vibration phase by a microprocessor. The high-power frequency-doubled Nd:YAG laser produces pulses containing up to 5 mJ of energy, which is amply sufficient to record single-shot holograms. As the laser pulse length is 8 ns and the smallest time step of the trigger electronics is 1 μs, vibration measurements of frequencies up to 250 kHz are achievable through this method, provided that the maximum vibration amplitude exceeds a few nanometers. In our application, middle ear mechanics, measuring frequencies extend from 5 Hz to 20 kHz. The experimental setup will be presented, as well as results of measurements on a stretched circular rubber membrane and a rabbit's eardrum. Two of the challenges when measuring biological tissues, such as the eardrum, are low reflectivity and fast dehydration. To increase reflectivity, a coating is applied and to counteract the undesirable effects of tissue dehydration, the measurement setup and software have been optimized for speed without

Physical mechanisms of megahertz vibrations and nonlinear detection in ultrasonic force and related microscopies

Energy Technology Data Exchange (ETDEWEB)

Bosse, J. L.; Huey, B. D. [Department of Materials Science and Engineering, 97 North Eagleville Road, Unit 3136, Storrs, Connecticut 06269-3136 (United States); Tovee, P. D.; Kolosov, O. V., E-mail: o.kolosov@lancaster.ac.uk [Department of Physics, Lancaster University, Lancaster LA1 4YB (United Kingdom)

2014-04-14

Use of high frequency (HF) vibrations at MHz frequencies in Atomic Force Microscopy (AFM) advanced nanoscale property mapping to video rates, allowed use of cantilever dynamics for mapping nanomechanical properties of stiff materials, sensing μs time scale phenomena in nanostructures, and enabled detection of subsurface features with nanoscale resolution. All of these methods critically depend on the generally poor characterized HF behaviour of AFM cantilevers in contact with a studied sample, spatial and frequency response of piezotransducers, and transfer of ultrasonic vibrations between the probe and a specimen. Focusing particularly on Ultrasonic Force Microscopy (UFM), this work is also applicable to waveguide UFM, heterodyne force microscopy, and near-field holographic microscopy, all methods that exploit nonlinear tip-surface force interactions at high frequencies. Leveraging automated multidimensional measurements, spectroscopic UFM (sUFM) is introduced to investigate a range of common experimental parameters, including piezotransducer excitation frequency, probed position, ultrasonic amplitude, cantilever geometry, spring constant, and normal force. Consistent with studies of influence of each of these factors, the data-rich sUFM signatures allow efficient optimization of ultrasonic-AFM based measurements, leading to best practices recommendations of using longer cantilevers with lower fundamental resonance, while at the same time increasing the central frequency of HF piezo-actuators, and only comparing results within areas on the order of few μm{sup 2} unless calibrated directly or compared with in-the-imaged area standards. Diverse materials such as Si, Cr, and photoresist are specifically investigated. This work thereby provides essential insight into the reliable use of MHz vibrations with AFM and provides direct evidence substantiating phenomena such as sensitivity to adhesion, diminished friction for certain ultrasonic conditions, and the

Physical mechanisms of megahertz vibrations and nonlinear detection in ultrasonic force and related microscopies

International Nuclear Information System (INIS)

Bosse, J. L.; Huey, B. D.; Tovee, P. D.; Kolosov, O. V.

2014-01-01

Use of high frequency (HF) vibrations at MHz frequencies in Atomic Force Microscopy (AFM) advanced nanoscale property mapping to video rates, allowed use of cantilever dynamics for mapping nanomechanical properties of stiff materials, sensing μs time scale phenomena in nanostructures, and enabled detection of subsurface features with nanoscale resolution. All of these methods critically depend on the generally poor characterized HF behaviour of AFM cantilevers in contact with a studied sample, spatial and frequency response of piezotransducers, and transfer of ultrasonic vibrations between the probe and a specimen. Focusing particularly on Ultrasonic Force Microscopy (UFM), this work is also applicable to waveguide UFM, heterodyne force microscopy, and near-field holographic microscopy, all methods that exploit nonlinear tip-surface force interactions at high frequencies. Leveraging automated multidimensional measurements, spectroscopic UFM (sUFM) is introduced to investigate a range of common experimental parameters, including piezotransducer excitation frequency, probed position, ultrasonic amplitude, cantilever geometry, spring constant, and normal force. Consistent with studies of influence of each of these factors, the data-rich sUFM signatures allow efficient optimization of ultrasonic-AFM based measurements, leading to best practices recommendations of using longer cantilevers with lower fundamental resonance, while at the same time increasing the central frequency of HF piezo-actuators, and only comparing results within areas on the order of few μm 2 unless calibrated directly or compared with in-the-imaged area standards. Diverse materials such as Si, Cr, and photoresist are specifically investigated. This work thereby provides essential insight into the reliable use of MHz vibrations with AFM and provides direct evidence substantiating phenomena such as sensitivity to adhesion, diminished friction for certain ultrasonic conditions, and the particular

Isotope separation using vibrationally excited molecules

International Nuclear Information System (INIS)

Woodroffe, J.A.; Keck, J.C.

1979-01-01

Vibrational excitation of molecules having components of a selected isotope type is used to produce a conversion from vibrational to translational excitation of the molecules by collision with the molecules of a heavy carrier gas. The resulting difference in translaton between the molecules of the selected isotope type and all other molecules of the same compound permits their separate collection. When applied to uranium enrichment, a subsonic cryogenic flow of molecules of uranium hexafluoride in combination with an argon carrier gas is directed through a cooled chamber that is illuminated by laser radiaton tuned to vibrationally excite the uranium hexafluoride molecules of a specific uranium isotope. The excited molecules collide with carrier gas molecules, causing a conversion of the excitation energy into a translation of the excited molecule, which results in a higher thermal energy or diffusivity than that of the other uranium hexafluoride molecules. The flowing molecules including the excited molecules directly enter a set of cryogenically cooled channels. The higher thermal velocity of the excited molecules increases the probability of their striking a collector surface. The molecules which strike this surface immediately condense. After a predetermined thickness of molecules is collected on the surface, the flow of uranium hexafluoride is interrupted and the chamber heated to the point of vaporization of the collected hexafluoride, permitting its removal. (LL)

Combined Ultrasonic Elliptical Vibration and Chemical Mechanical Polishing of Monocrystalline Silicon

Directory of Open Access Journals (Sweden)

Liu Defu

2016-01-01

Full Text Available An ultrasonic elliptical vibration assisted chemical mechanical polishing(UEV-CMP is employed to achieve high material removal rate and high surface quality in the finishing of hard and brittle materials such as monocrystalline silicon, which combines the functions of conventional CMP and ultrasonic machining. In theultrasonic elliptical vibration aided chemical mechanical polishingexperimental setup developed by ourselves, the workpiece attached at the end of horn can vibrate simultaneously in both horizontal and vertical directions. Polishing experiments are carried out involving monocrystalline silicon to confirm the performance of the proposed UEV-CMP. The experimental results reveal that the ultrasonic elliptical vibration can increase significantly the material removal rate and reduce dramatically the surface roughness of monocrystalline silicon. It is found that the removal rate of monocrystalline silicon polished by UEV-CMP is increased by approximately 110% relative to that of conventional CMP because a passive layer on the monocrystalline silicon surface, formed by the chemical action of the polishing slurry, will be removed not only by the mechanical action of CMP but also by ultrasonic vibration action. It indicates that the high efficiency and high quality CMP of monocrystalline silicon can be performed with the proposed UEV-CMP technique.

Surface enhanced Raman spectroscopic studies on aspirin : An experimental and theoretical approach

International Nuclear Information System (INIS)

Premkumar, R.; Premkumar, S.; Parameswari, A.; Mathavan, T.; Benial, A. Milton Franklin; Rekha, T. N.

2016-01-01

Surface enhanced Raman scattering (SERS) studies on aspirin molecule adsorbed on silver nanoparticles (AgNPs) were investigated by experimental and density functional theory approach. The AgNPs were synthesized by the solution-combustion method and characterized by the X-ray diffraction and high resolution-transmission electron microscopy techniques. The averaged particle size of synthesized AgNPs was calculated as ∼55 nm. The normal Raman spectrum (nRs) and SERS spectrum of the aspirin were recorded. The molecular structure of the aspirin and aspirin adsorbed on silver cluster were optimized by the DFT/ B3PW91 method with LanL2DZ basis set. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation. The calculated nRs and SERS frequencies were correlated well with the observed frequencies. The flat-on orientation was predicted from the nRs and SERS spectra, when the aspirin adsorbed on the AgNPs. Hence, the present studies lead to the understanding of adsorption process of aspirin on the AgNPs, which paves the way for biomedical applications.

Surface enhanced Raman spectroscopic studies on aspirin : An experimental and theoretical approach

Energy Technology Data Exchange (ETDEWEB)

Premkumar, R.; Premkumar, S.; Parameswari, A.; Mathavan, T.; Benial, A. Milton Franklin, E-mail: miltonfranklin@yahoo.com [Department of Physics, N.M.S.S.V.N College, Madurai-625019, Tamilnadu, India. (India); Rekha, T. N. [PG and Research Department of Physics, Lady Doak College, Madurai-625 002, Tamilnadu, India. (India)

2016-05-06

Surface enhanced Raman scattering (SERS) studies on aspirin molecule adsorbed on silver nanoparticles (AgNPs) were investigated by experimental and density functional theory approach. The AgNPs were synthesized by the solution-combustion method and characterized by the X-ray diffraction and high resolution-transmission electron microscopy techniques. The averaged particle size of synthesized AgNPs was calculated as ∼55 nm. The normal Raman spectrum (nRs) and SERS spectrum of the aspirin were recorded. The molecular structure of the aspirin and aspirin adsorbed on silver cluster were optimized by the DFT/ B3PW91 method with LanL2DZ basis set. The vibrational frequencies were calculated and assigned on the basis of potential energy distribution calculation. The calculated nRs and SERS frequencies were correlated well with the observed frequencies. The flat-on orientation was predicted from the nRs and SERS spectra, when the aspirin adsorbed on the AgNPs. Hence, the present studies lead to the understanding of adsorption process of aspirin on the AgNPs, which paves the way for biomedical applications.

Investigation into structure and dehydration dynamic of gallic acid monohydrate: A Raman spectroscopic study.

Science.gov (United States)

Cai, Qiang; Xue, Jiadan; Wang, Qiqi; Du, Yong

2018-05-02

The dehydration process of gallic acid monohydrate was carried out by heating method and characterized using Raman spectroscopic technique. Density functional theory calculation with B3LYP function is applied to simulate optimized structures and vibrational frequencies of anhydrous gallic acid and its corresponding monohydrated form. Different vibrational modes are assigned by comparison between experimental and theoretical Raman spectra of above two polymorphs. Raman spectra show that vibrational modes of the monohydrate are distinctively different from those of anhydrous one. Meanwhile, the dynamic information about dehydration process of gallic acid monohydrate could also be observed and monitored directly with the help of Raman spectral analysis. The decay rate of the characteristic band from gallic acid monohydrate and the growth rate of anhydrous one are pretty consistent with each other. It indicates that there is no intermediate present during the dehydration process of gallic acid monohydrate. The results could offer us benchmark works for identifying both anhydrous and hydrated pharmaceutical compounds, characterizing their corresponding molecular conformation within various crystalline forms, and also providing useful information about the process of dehydration dynamic at the microscopic molecular level. Copyright © 2018 Elsevier B.V. All rights reserved.

Proposals of electronic-vibrational energy relaxation studies by using laser pulses synchronized with IR-SR pulses

International Nuclear Information System (INIS)

Nakagawa, Hideyuki

2000-01-01

Synchrotron radiation is expected to be the sharp infrared light source for the advanced experiments on IR and FIR spectroscopy in wide research fields. Especially, synchronized use of SR with VIS and/or UV laser light is to be a promising technique for the research on the dynamical properties of the photo-excited states in condensed materials. Some proposals are attempted for high resolution IR spectroscopy to elucidate fine interaction of molecular ions in crystalline solids with their environmental field and for time-resolved IR spectroscopic studies on the electronic and vibrational energy relaxation by using laser pulses synchronized with IR-SR pulses. Several experimental results are presented in relevance to the subjects; on high-resolution FTIR spectra of cyanide ions and metal cyanide complexes in cadmium halide crystals, on the energy up-conversion process among the vibrational levels of cyanide ions in alkali halide crystals, and on the electronic-to-vibrational energy conversion process in metal cyanide complexes. (author)

Vibrational Fingerprints of Low-Lying PtnP2n (n = 1–5) Cluster Structures from Global Optimization Based on Density Functional Theory Potential Energy Surfaces

KAUST Repository

Jedidi, Abdesslem; Li, Rui; Fornasiero, Paolo; Cavallo, Luigi; Carbonniere, Philippe

2015-01-01

Vibrational fingerprints of small PtnP2n (n = 1–5) clusters were computed from their low-lying structures located from a global exploration of their DFT potential energy surfaces with the GSAM code. Five DFT methods were assessed from the CCSD(T) wavenumbers of PtP2 species and CCSD relative energies of Pt2P4 structures. The eight first PtnP2n isomers found are reported. The vibrational computations reveal (i) the absence of clear signatures made by overtone or combination bands due to very weak mechanical and electrical anharmonicities and (ii) some significant and recurrent vibrational fingerprints in correlation with the different PP bonding situations in the PtnP2n structures.

Vibrational Fingerprints of Low-Lying PtnP2n (n = 1–5) Cluster Structures from Global Optimization Based on Density Functional Theory Potential Energy Surfaces

KAUST Repository

Jedidi, Abdesslem

2015-11-13

Vibrational fingerprints of small PtnP2n (n = 1–5) clusters were computed from their low-lying structures located from a global exploration of their DFT potential energy surfaces with the GSAM code. Five DFT methods were assessed from the CCSD(T) wavenumbers of PtP2 species and CCSD relative energies of Pt2P4 structures. The eight first PtnP2n isomers found are reported. The vibrational computations reveal (i) the absence of clear signatures made by overtone or combination bands due to very weak mechanical and electrical anharmonicities and (ii) some significant and recurrent vibrational fingerprints in correlation with the different PP bonding situations in the PtnP2n structures.

Studies on the substrate mediated vibrational excitation of CO/Si(100) by means of SFG spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Han, Xu; Lass, Kristian; Balgar, Thorsten; Hasselbrink, Eckart [Universitaet Duisburg-Essen, Fachbereich Chemie, 45117 Essen (Germany)

2009-07-01

Vibrational excitations of adsorbates play an important role in chemical reaction dynamics. In the past decade CO on solid surfaces was chosen as adequate model system for studying vibrational relaxation dynamics. Our work is focused on the energy dissipation of vibrationally excited CO adsorbed on a silicon surface by means of IR/Vis sum frequency generation (SFG) spectroscopy. Here we present studies on substrate mediated excitation of vibrational modes of CO on Si(100) induced by UV radiation. We suppose the observation of highly excited internal stretch vibrations of CO caused by hot electrons generated within the silicon substrate.

Nonlinear spectroscopic studies of interfacial molecular ordering

International Nuclear Information System (INIS)

Superfine, R.

1991-07-01

The second order nonlinear optical processes of second harmonic generation and sum frequency generation are powerful new probes of surfaces. They possess unusual surface sensitivity due to the symmetry properties of the nonlinear susceptibility. In particular, infrared-visible sum frequency generation (SFG) can obtain the vibrational spectrum of sub-monolayer coverages of molecules. In this thesis, we explore the unique information that can be obtained from SFG. We take advantage of the sensitivity of SFG to the conformation of alkane chains to study the interaction between adsorbed liquid crystal molecules and surfactant treated surfaces. The sign of the SFG susceptibility depends on the sign of the molecular polarizability and the orientation, up or down, of the molecule. We experimentally determine the sign of the susceptibility and use it to determine the absolute orientation to obtain the sign of the molecular polarizability and show that this quantity contains important information about the dynamics of molecular charge distributions. Finally, we study the vibrational spectra and the molecular orientation at the pure liquid/vapor interface of methanol and water and present the most detailed evidence yet obtained for the structure of the pure water surface. 32 refs., 4 figs., 2 tabs

Optical spectroscopic methods for probing the conformational stability of immobilised enzymes.

Science.gov (United States)

Ganesan, Ashok; Moore, Barry D; Kelly, Sharon M; Price, Nicholas C; Rolinski, Olaf J; Birch, David J S; Dunkin, Ian R; Halling, Peter J

2009-07-13

We report the development of biophysical techniques based on circular dichroism (CD), diffuse reflectance infrared Fourier transform (DRIFT) and tryptophan (Trp) fluorescence to investigate in situ the structure of enzymes immobilised on solid particles. Their applicability is demonstrated using subtilisin Carlsberg (SC) immobilised on silica gel and Candida antartica lipase B immobilised on Lewatit VP.OC 1600 (Novozyme 435). SC shows nearly identical secondary structure in solution and in the immobilised state as evident from far UV CD spectra and amide I vibration bands. Increased near UV CD intensity and reduced Trp fluorescence suggest a more rigid tertiary structure on the silica surface. After immobilised SC is inactivated, these techniques reveal: a) almost complete loss of near UV CD signal, suggesting loss of tertiary structure; b) a shift in the amide I vibrational band from 1658 cm(-1) to 1632 cm(-1), indicating a shift from alpha-helical structure to beta-sheet; c) a substantial blue shift and reduced dichroism in the far UV CD, supporting a shift to beta-sheet structure; d) strong increase in Trp fluorescence intensity, which reflects reduced intramolecular quenching with loss of tertiary structure; and e) major change in fluorescence lifetime distribution, confirming a substantial change in Trp environment. DRIFT measurements suggest that pressing KBr discs may perturb protein structure. With the enzyme on organic polymer it was possible to obtain near UV CD spectra free of interference by the carrier material. However, far UV CD, DRIFT and fluorescence measurements showed strong signals from the organic support. In conclusion, the spectroscopic methods described here provide structural information hitherto inaccessible, with their applicability limited by interference from, rather than the particulate nature of, the support material.

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

Science.gov (United States)

Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

2015-05-01

The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader's quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN (1Σ) and hydrideisocyanidezinc HZnNC (1Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]+ composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn+ (2Σ) and HCNZn+ (2Σ).

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

International Nuclear Information System (INIS)

Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen

2015-01-01

The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ( 1 Σ) and hydrideisocyanidezinc HZnNC ( 1 Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn] + composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn + ( 2 Σ) and HCNZn + ( 2 Σ)

Structure and spectroscopic properties of neutral and cationic tetratomic [C,H,N,Zn] isomers: A theoretical study

Energy Technology Data Exchange (ETDEWEB)

Redondo, Pilar; Largo, Antonio; Vega-Vega, Álvaro; Barrientos, Carmen, E-mail: cbb@qf.uva.es [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid (Spain)

2015-05-14

The structure and spectroscopic parameters of the most relevant [C,H,N,Zn] isomers have been studied employing high-level quantum chemical methods. For each isomer, we provide predictions for their molecular structure, thermodynamic stabilities as well as vibrational and rotational spectroscopic parameters which could eventually help in their experimental detection. In addition, we have carried out a detailed study of the bonding situations by means of a topological analysis of the electron density in the framework of the Bader’s quantum theory of atoms in molecules. The analysis of the relative stabilities and spectroscopic parameters suggests two linear isomers of the neutral [C,H,N,Zn] composition, namely, cyanidehydridezinc HZnCN ({sup 1}Σ) and hydrideisocyanidezinc HZnNC ({sup 1}Σ), as possible candidates for experimental detections. For the cationic [C,H,N,Zn]{sup +} composition, the most stable isomers are the ion-molecule complexes arising from the direct interaction of the zinc cation with either the nitrogen or carbon atom of either hydrogen cyanide or hydrogen isocyanide, namely, HCNZn{sup +} ({sup 2}Σ) and HCNZn{sup +} ({sup 2}Σ)

Report of workshop on vibration related to fluid in atomic energy field. 4

International Nuclear Information System (INIS)

1993-01-01

This is the fourth workshop on the vibration related to fluid in atomic energy field of Yayoi research group. This time, two topics were taken up. One is edgetone phenomena and the liquid surface vibration phenomena due to flow. Another is the introduction of the experience in light water reactors. The workshop was held on August 30 and 31, 1993 at Nuclear Engineering Research Laboratory, University of Tokyo. At the workshop, lectures were given on the mechanism of occurrence of edgetone, the theoretical analysis of edgetone and edgenoise, the self-excited vibration of free liquid surface due to vertical plane jet and vertical cylindrical jet, the research on flow instability phenomena in parallel loop system, the irregular vibration behavior of U-shaped tubes excited by flow, the research on the vibration of cyclindrical weir due to fluid discharge, the examples of the vibration related to fluid in LWRs, the estimation of fatigue phenomena in bearing rings, the vibration of rotary vanes and verifying test, the analysis of flow in isolated phase bus plate vane and the measurement of velocity distribution, flow in piping and the behavior of valve vibration, the condition for the occurrence of flow vibration in the main steam separation valve of BWR, the vibration of piping due to orifice, the analysis of flow in two-dimensional vibrating cascade, and the subjects of fluid vibration assessment in atomic energy. (K.I.)

Damage and failure detection of composites using optical fiber vibration sensor

International Nuclear Information System (INIS)

Yang, Y. C.; Han, K. S.

2001-01-01

An intensity-based optical fiber vibration sensor is applied to detect and evaluate damages and fiber failure of composites. The optical fiber vibration sensor is constructed by placing two cleaved fiber end, one of which is cantilevered in a hollow glass tube. The movement of the cantilevered section lags behind the rest of the sensor in response to an applied vibration and the amount of light coupled between the two fibers is thereby modulated. Vibration characteristics of the optical fiber vibration sensor are investigated. Surface mounted optical fiber vibration sensor is used in tensile and indentation test. Experimental results show that the optical fiber sensor can detect damages and fiber failure of composites correctly

The dance of molecules: new dynamical perspectives on highly excited molecular vibrations.

Science.gov (United States)

Kellman, Michael E; Tyng, Vivian

2007-04-01

At low energies, molecular vibrational motion is described by the normal modes model. This model breaks down at higher energy, with strong coupling between normal modes and onset of chaotic dynamics. New anharmonic modes are born in bifurcations, or branchings of the normal modes. Knowledge of these new modes is obtained through the window of frequency-domain spectroscopy, using techniques of nonlinear classical dynamics. It may soon be possible to "watch" molecular rearrangement reactions spectroscopically. Connections are being made with reaction rate theories, condensed phase systems, and motions of electrons in quantum dots.

Effects of aging on vibration detection thresholds at various body regions

Directory of Open Access Journals (Sweden)

Walsh Natalie

2003-02-01

Full Text Available Abstract Background The ability to detect sinusoidal vibrations on the skin surface is dependent on the activation of two classes of receptors. The density of such receptors varies across the skin surface and is a factor in determining the sensory acuity of each skin area. However, the acuity of many sensory systems is known to deteriorate with advancing age. The aim of this study was to determine if vibrotactile sensibility of several skin surfaces deteriorated equally with advancing age. Methods Vibration detection thresholds for two frequencies of vibration (30 Hz and 200 Hz were determined using a method of limits protocol, in two groups of healthy adults, one group aged 17 to 27 years and the other aged 55 to 90 years. Sinusoidal vibrations were generated by a computer and delivered to the skin surface via the probe (diameter = 2 mm of a mechanical vibrator. Four skin sites (palmar surface of the tip of the middle finger, volar surface of the forearm, lateral aspect of the shoulder, cheek just caudal to the zygoma were tested. Results The fingertip was the most sensitive site for vibrotactile detection at both frequencies in a substantial majority of subjects. The older group of subjects showed significantly higher detection thresholds for both frequencies at all sites, except the fingertip, when compared to young subjects. Conclusion The study confirms the deterioration of vibrotactile acuity at several skin sites previously reported in the literature. However, there appears to be no significant reduction in vibrotactile detection at the fingertips in older subjects. This may reflect the high receptor density of this area, or the functional importance of vibrotactile sensibility of the fingertips or some combination of both of these factors.

Raman spectroscopic analyses of preserved historical specimens of human hair attributed to Robert Stephenson and Sir Isaac Newton.

Science.gov (United States)

Edwards, Howell G M; Hassan, Nik F N; Wilson, Andrew S

2004-10-01

The Raman spectra of two historical specimens of human hair attributed to the engineer Robert Stephenson and scientist Sir Isaac Newton, preserved in private collections are reported. Comparisons are made with the Raman spectra of modern hair specimens and with hair from archaeological excavations. The hair spectra collected with a laser excitation of 785 nm are of a better quality than those collected using 1064 nm. The historical hair specimens are remarkably well-defined spectroscopically in terms of the amide I vibrational mode and the [small nu](SS), ascribed to a predominantly gauche-gauche-gauche CSSC conformation. The contrast with degraded hair specimens recovered from archaeological excavations is striking. The presence of a weak feature near 2590 cm(-1) in the hair samples attributed to a [small nu](SH) vibration could be indicative of a reduction process operative on the CSSC cystine keratotic linkages and a possible origin of this is bacterial biodegradation identified histologically. This study demonstrates the molecular information available from non-destructive Raman spectroscopic analysis from single hair shafts or small bundles of fibres which complements information available from histological and destructive analytical techniques for rare biological specimens subjected to conservation or curation procedures in museums or private collections.

Analysis of micro vibration in gas film of aerostatic guide way based on molecule collision theory

Directory of Open Access Journals (Sweden)

Yang Shao Hua

2016-01-01

Full Text Available Micro vibration of the aerostatic guide way has a significant impact on its dynamic characteristics and stability, which limits the development of pneumatic component. High pressure gas molecules have been collided with the supporting surface and the internal surface of the throttle during the flow process. Variable impulse of the surfaces aside for the gas film are affected by the changes of impulse which formed irregular impact force in horizontal and vertical direction. Micro-vibration takes place based on the natural frequency of the system and its frequency doubling. In this paper, the vibration model was established to describe the dynamic characteristics of the gas film, and the formation mechanism of micro vibration in the film is defined. Through the simulation analysis and experimental comparison, formation mechanism of the micro vibration in the gas film is confirmed. It was proposed that the micro vibration of gas film can be produced no matter whether there is a gas chamber or not in the throttle. Under the same conditions, the micro vibration of the guide way with air chamber is greater than that without any chamber. The frequency points of the vibration peaks are almost the same, as well as the vibration pattern in the frequency domain.

Vibration suppression in cutting tools using collocated piezoelectric sensors/actuators with an adaptive control algorithm

Energy Technology Data Exchange (ETDEWEB)

Radecki, Peter P [Los Alamos National Laboratory; Farinholt, Kevin M [Los Alamos National Laboratory; Park, Gyuhae [Los Alamos National Laboratory; Bement, Matthew T [Los Alamos National Laboratory

2008-01-01

The machining process is very important in many engineering applications. In high precision machining, surface finish is strongly correlated with vibrations and the dynamic interactions between the part and the cutting tool. Parameters affecting these vibrations and dynamic interactions, such as spindle speed, cut depth, feed rate, and the part's material properties can vary in real-time, resulting in unexpected or undesirable effects on the surface finish of the machining product. The focus of this research is the development of an improved machining process through the use of active vibration damping. The tool holder employs a high bandwidth piezoelectric actuator with an adaptive positive position feedback control algorithm for vibration and chatter suppression. In addition, instead of using external sensors, the proposed approach investigates the use of a collocated piezoelectric sensor for measuring the dynamic responses from machining processes. The performance of this method is evaluated by comparing the surface finishes obtained with active vibration control versus baseline uncontrolled cuts. Considerable improvement in surface finish (up to 50%) was observed for applications in modern day machining.

Surface Effect on Vibration of Y-SWCNTs Embedded on Pasternak Foundation Conveying Viscose Fluid

Directory of Open Access Journals (Sweden)

A. Ghorbanpour-Arani

2015-01-01

Full Text Available Surface and small scale effects on free transverse vibration of a single-walled carbon nanotube (SWCNT fitted with Y-junction at downstream end conveying viscose fluid is investigated in this article based on Euler-Bernoulli beam (EBB model. Nonlocal elasticity theory is employed to consider small scale effects due to its simplicity and efficiency. The energy method and Hamilton’s principle are used to establish the corresponding motion equation. To discretize and solve the governing equation of motion the Galerkin method is applied. Moreover, the small-size effect, angle of Y-junction, surface layer and Pasternak elastic foundation are studied in detail. Regarding fluid flow effects, it has been concluded that the fluid flow is an effective factor on increasing the instability of Y-SWCNT. Results show that increasing the angle of Y-junction enhances the flutter fluid velocity where the first and second modes are merged. This work could be used in medical application and design of nano-electromechanical devices such as measuring the density of blood flowing through such nanotubes.

Effect of structural design on traffic-induced building vibrations

DEFF Research Database (Denmark)

Persson, Peter; Andersen, Lars Vabbersgaard; Persson, Kent

2017-01-01

Population growth and urbanization results in densified cities, where new buildings are being built closer to existing vibration sources such as road-, tram- and rail traffic. In addition, new transportation systems are constructed closer to existing buildings. Potential disturbing vibrations...... are one issue to consider in planning urban environment and densification of cities. Vibrations can be disturbing for humans but also for sensitive equipment in, for example, hospitals. In determining the risk for disturbing vibrations, the distance between the source and the receiver, the ground...... properties, and type and size of the building are governing factors. In the paper, a study is presented aiming at investigating the influence of various parameters of the building's structural design on vibration levels in the structure caused by ground surface loads, e.g. traffic. Parameters studied...

Molecular structure and spectroscopic properties of 4-nitrocatechol at different pH: UV-visible, Raman, DFT and TD-DFT calculations

International Nuclear Information System (INIS)

Cornard, Jean-Paul; Rasmiwetti; Merlin, Jean-Claude

2005-01-01

We investigated theoretically, by density functional theoretical calculations and by vibrational and electronic spectroscopies, the structure and the molecular spectroscopic properties of the 4-nitrocatechol molecule with varying pH. The lower energy stable structures of the neutral, monoanion and dianion forms were compared, and influence of water solvation was examined. The Raman and UV-visible spectra of 4-nitrocatechol and of its singly deprotonated form were recorded by varying the pH from 2 to 9. A calculation of the vibrational frequencies has allowed a complete assignment of the Raman spectra of the two forms of 4-nitrocatechol, and has permitted to investigate the evolution of vibrational normal modes upon deprotonation. Based on the molecular orbital analysis and the time dependent DFT (TD-DFT) calculations, we discussed the electronic structure and the assignment of the absorption bands in the electronic spectra of 4-nitrocatechol and mono-deprotonated 4-nitrocatechol

Detection of surface cracking in steel pipes based on vibration data using a multi-class support vector machine classifier

Science.gov (United States)

Mustapha, S.; Braytee, A.; Ye, L.

2017-04-01

In this study, we focused at the development and verification of a robust framework for surface crack detection in steel pipes using measured vibration responses; with the presence of multiple progressive damage occurring in different locations within the structure. Feature selection, dimensionality reduction, and multi-class support vector machine were established for this purpose. Nine damage cases, at different locations, orientations and length, were introduced into the pipe structure. The pipe was impacted 300 times using an impact hammer, after each damage case, the vibration data were collected using 3 PZT wafers which were installed on the outer surface of the pipe. At first, damage sensitive features were extracted using the frequency response function approach followed by recursive feature elimination for dimensionality reduction. Then, a multi-class support vector machine learning algorithm was employed to train the data and generate a statistical model. Once the model is established, decision values and distances from the hyper-plane were generated for the new collected data using the trained model. This process was repeated on the data collected from each sensor. Overall, using a single sensor for training and testing led to a very high accuracy reaching 98% in the assessment of the 9 damage cases used in this study.

Influence of vibrations on heat-exchanger tubes. A literature survey

International Nuclear Information System (INIS)

Oddving, B.; Wiberg, J.

1965-05-01

During the last few years vibrations in heat-exchanger tubes have become a more and more serious problem due to increased demands for higher capacities of such components, which, for example, are included in nuclear power plants. These vibrations, which are most frequently induced by vortex shedding in the flow around the tubes, may sometimes cause impact fretting on the tubes and/or baffles where they are in contact with each other. Fretting may occur when two surfaces rub against each other under the influence of a vibrating movement, whereby the amplitudes are rather small (<0.25 mm). Some laboratory experiments have been reported with a combined impact and sliding movement, which is supposed to take place in heat exchangers. The influences of the clearance between the tube and baffle-hole surfaces, pressure normal to the contact surface, amplitude, frequency, time, atmosphere (also water) have been investigated for various material combinations. The finish of the tube and baffle-hole surfaces as well as the shape of the latter may also have an influence on the fretting phenomenon. However, any results from research on this matter have not been found in the literature so far. There are always difficulties in translating the above mentioned laboratory results into real operating conditions. In order to be able to judge whether a given heat exchanger might be subject to vibrational damages or not a few researchers have derived correlations between different flow-, design- and material parameters. That, on the basis of the design and actual operating conditions calculated value of such a correlation, will then indicate the risk of damages due to tube vibrations. (author)

The pH dependent Raman spectroscopic study of caffeine

Science.gov (United States)

Kang, Jian; Gu, Huaimin; Zhong, Liang; Hu, Yongjun; Liu, Fang

2011-02-01

First of all the surface enhanced Raman spectroscopy (SERS) and normal Raman spectra of caffeine aqueous solution were obtained at different pH values. In order to obtain the detailed vibrational assignments of the Raman spectroscopy, the geometry of caffeine molecule was optimized by density functional theory (DFT) calculation. By comparing the SERS of caffeine with its normal spectra at different pH values; it is concluded that pH value can dramatically affect the SERS of caffeine, but barely affect the normal Raman spectrum of caffeine aqueous solution. It can essentially affect the reorientation of caffeine molecule to the Ag colloid surface, but cannot impact the vibration of functional groups and chemical bonds in caffeine molecule.

Raman and Terahertz Spectroscopic Investigation of Cocrystal Formation Involving Antibiotic Nitrofurantoin Drug and Coformer 4-aminobenzoic Acid

Directory of Open Access Journals (Sweden)

Yong Du

2016-12-01

Full Text Available Cocrystallization could improve most physicochemical properties of specific active pharmaceutical ingredients, which has great potential in pharmaceutical development. In this study, the cocrystal of nitrofurantoin and 4-aminobenzoic acid was prepared with solid-state (solvent-free or green-chemistry grinding approach, and the above cocrystal has been characterized by Raman and terahertz vibrational spectroscopic techniques. Spectral results show that the vibrational modes of the cocrystal within the whole spectral region are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman spectra. These results offer us unique means for characterizing the cocrystal conformation from the molecule-level, and provides us with rich information about the reaction dynamic of cocrystal formation within pharmaceutical fields.

Conformational, vibrational, NMR and DFT studies of N-methylacetanilide.

Science.gov (United States)

Arjunan, V; Santhanam, R; Rani, T; Rosi, H; Mohan, S

2013-03-01

A detailed conformational, vibrational, NMR and DFT studies of N-methylacetanilide have been carried out. In DFT, B3LYP method have been used with 6-31G(**), 6-311++G(**) and cc-pVTZ basis sets. The vibrational frequencies were calculated resulting in IR and Raman frequencies together with intensities and Raman depolarisation ratios. The dipole moment derivatives were computed analytically. Owing to the complexity of the molecule, the potential energy distributions of the vibrational modes of the compound are also calculated. Isoelectronic molecular electrostatic potential surface (MEP) and electron density surface were examined. (1)H and (13)C NMR isotropic chemical shifts were calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound were also determined from TD-DFT method. Copyright © 2012 Elsevier B.V. All rights reserved.

Optimum Design of a Helicopter Rotor for Low Vibration Using Aeroelastic Analysis and Response Surface Methods

Science.gov (United States)

Ganguli, R.

2002-11-01

An aeroelastic analysis based on finite elements in space and time is used to model the helicopter rotor in forward flight. The rotor blade is represented as an elastic cantilever beam undergoing flap and lag bending, elastic torsion and axial deformations. The objective of the improved design is to reduce vibratory loads at the rotor hub that are the main source of helicopter vibration. Constraints are imposed on aeroelastic stability, and move limits are imposed on the blade elastic stiffness design variables. Using the aeroelastic analysis, response surface approximations are constructed for the objective function (vibratory hub loads). It is found that second order polynomial response surfaces constructed using the central composite design of the theory of design of experiments adequately represents the aeroelastic model in the vicinity of the baseline design. Optimization results show a reduction in the objective function of about 30 per cent. A key accomplishment of this paper is the decoupling of the analysis problem and the optimization problems using response surface methods, which should encourage the use of optimization methods by the helicopter industry.

Synchrotron radiation in the Far-Infrared: Adsorbate-substrate vibrations and resonant interactions

International Nuclear Information System (INIS)

Hoffmann, F.M.; Williams, G.P.; Hirschmugl, C.J.; Chabal, Y.J.

1991-01-01

Synchrotron radiation in the Far Infrared offers the potential for a broadband source of high brightness and intensity. Recent development of a Far-Infrared Beamline at the NSLS in Brookhaven provides an unique high intensity source in the FIR spectral range (800-10 cm -1 ). This talk reviews its application to surface vibrational spectroscopy of low frequency adsorbate-substrate vibrations and resonant interactions on metal surfaces

Spectroscopic measurement of H(1S) and H sub 2 (v double prime ,J double prime ) in an H sup minus ion source plasma

Energy Technology Data Exchange (ETDEWEB)

Stutzin, G.C.

1990-08-01

Low pressure H{sub 2} discharges have been used for some time as sources of H{sup {minus}} ions. These discharges contain many different species of particles which interact with each other and with the walls of the discharge chamber. Models exist that predict the populations of the various species for given macroscopic discharge parameters. However, many of the cross sections and wall catalyzation coefficients are unknown or somewhat uncertain. Therefore, it is of interest to measure the populations of as many of these species as possible, in order to determine the validity of the models. These models predict that H{sup {minus}} is created predominantly by the two-step process of vibrational excitation of hydrogen molecules followed by dissociative attachment of slow electrons to these vibrationally-excited hydrogen molecules. Many different collisional processes must be included in the models to explain the dependence of the various populations upon macroscopic parameters. This work presents results of spectroscopic measurements of the density and translational temperature of hydrogen atoms and of specific rotationally- and vibrationally-excited states of electronic ground-state H{sub 2}, in a discharge optimized for H{sup {minus}} production, as well as conventional measurements of the various charged species within the plasma. The spectroscopic measurements are performed directly by narrowband, single-photon absorption in the vacuum ultraviolet.

Recent advances in ion and electron spectroscopy of polymer surfaces

Science.gov (United States)

Gardella, Joseph A.

1988-01-01

The structure of microdomains and bonding at multicomponent polymer material interfaces has been studied using a variety of surface sensitive spectroscopic techniques. In our laboratory, low energy ion scattering spectroscopy (ISS) and static secondary ion mass spectrometry (SIMS) serve to complement results from angular dependent X-ray photoelectron spectroscopy (XPS or ESCA), Fourier transform infrared (FTIR) with attenuated total reflectance (ATR) sampling and SEM techniques to provide a quantitative picture of the relationships between structure, bonding, morphology and microdomain formation in near surface regions of polymeric systems. The added surface sensitivity of ISS can yield quantitative information at a sampling depth of 3-5 Å, which, with ESCA and FTIR analysis yields a "non-destructive" depth profile of domain formation in copolymer and blend systems. These studies will be illustrated with results from siloxane and siloxane/polycarbonate copolymer systems, where a complete picture of surface domain formation and morphology as a function of composition and polymer crystallinity has been developed. ISS can also yield information regarding the orientation of surface functional groups which ESCA and FTIR do not have either sensitivity and/or sufficient detection limits to analyze. These studies will be illustrated by the analysis of plasma hydrolysis/oxidation of stereoregular poly(methyl-methacrylate). The effects of functional group orientation on reactivity will be explored using results from ISS, ESCA and FTIR for stereoregular (isotatic, syndiotactic) and random (atactic) PMMA. Electron energy loss spectroscopy at high resolution (HREELS) has recently been extended to the examination of polymer and organic surfaces. Vibrational information from this experiment can yield very precise results about surface functional groups (1-20 Å) but at much lower resolution than is typical from IR and Raman techniques. However, the promise of evaluating surface

Vibrational Fingerprints of Low-Lying Pt(n)P(2n) (n = 1-5) Cluster Structures from Global Optimization Based on Density Functional Theory Potential Energy Surfaces.

Science.gov (United States)

Jedidi, Abdesslem; Li, Rui; Fornasiero, Paolo; Cavallo, Luigi; Carbonniere, Philippe

2015-12-03

Vibrational fingerprints of small Pt(n)P(2n) (n = 1-5) clusters were computed from their low-lying structures located from a global exploration of their DFT potential energy surfaces with the GSAM code. Five DFT methods were assessed from the CCSD(T) wavenumbers of PtP2 species and CCSD relative energies of Pt2P4 structures. The eight first Pt(n)P(2n) isomers found are reported. The vibrational computations reveal (i) the absence of clear signatures made by overtone or combination bands due to very weak mechanical and electrical anharmonicities and (ii) some significant and recurrent vibrational fingerprints in correlation with the different PP bonding situations in the Pt(n)P(2n) structures.

The effects of vibration-reducing gloves on finger vibration

Science.gov (United States)

Welcome, Daniel E.; Dong, Ren G.; Xu, Xueyan S.; Warren, Christopher; McDowell, Thomas W.

2015-01-01

Vibration-reducing (VR) gloves have been used to reduce the hand-transmitted vibration exposures from machines and powered hand tools but their effectiveness remains unclear, especially for finger protection. The objectives of this study are to determine whether VR gloves can attenuate the vibration transmitted to the fingers and to enhance the understanding of the mechanisms of how these gloves work. Seven adult male subjects participated in the experiment. The fixed factors evaluated include hand force (four levels), glove condition (gel-filled, air bladder, no gloves), and location of the finger vibration measurement. A 3-D laser vibrometer was used to measure the vibrations on the fingers with and without wearing a glove on a 3-D hand-arm vibration test system. This study finds that the effect of VR gloves on the finger vibration depends on not only the gloves but also their influence on the distribution of the finger contact stiffness and the grip effort. As a result, the gloves increase the vibration in the fingertip area but marginally reduce the vibration in the proximal area at some frequencies below 100 Hz. On average, the gloves reduce the vibration of the entire fingers by less than 3% at frequencies below 80 Hz but increase at frequencies from 80 to 400 Hz. At higher frequencies, the gel-filled glove is more effective at reducing the finger vibration than the air bladder-filled glove. The implications of these findings are discussed. Relevance to industry Prolonged, intensive exposure to hand-transmitted vibration can cause hand-arm vibration syndrome. Vibration-reducing gloves have been used as an alternative approach to reduce the vibration exposure. However, their effectiveness for reducing finger-transmitted vibrations remains unclear. This study enhanced the understanding of the glove effects on finger vibration and provided useful information on the effectiveness of typical VR gloves at reducing the vibration transmitted to the fingers. The new

Vibrational spectroscopy and structural analysis of complex uranium compounds (review)

International Nuclear Information System (INIS)

Umreiko, D.S.; Nikanovich, M.V.

1985-01-01

The paper reports on the combined application of experimental and theoretical methods of vibrational spectroscopy together with low-temperature luminescence data to determine the characteristic features of the formation and structure of complex systems, not only containing ligands directly coordinated to the CA uranium, but also associated with the extraspherical polyatomic electrically charged particles: organic cations. These include uranyl complexes and heterocyclical amines. Studied here were compounds of tetra-halouranylates with pyridine and its derivates, as well as dipyridyl, quinoline and phenanthroline. Structural schemes are also proposed for other uranyl complexes with protonated heterocyclical amines with a more complicated composition, which correctly reflect their spectroscopic properties

Spectroscopic analysis of 8-hydroxyquinoline derivatives and investigation of its reactive properties by DFT and molecular dynamics simulations

Science.gov (United States)

Sureshkumar, B.; Mary, Y. Sheena; Resmi, K. S.; Panicker, C. Yohannan; Armaković, Stevan; Armaković, Sanja J.; Van Alsenoy, C.; Narayana, B.; Suma, S.

2018-03-01

Two 8-hydroxyquinoline derivatives, 5,7-dichloro-8-hydroxyquinoline (57DC8HQ) and 5-chloro-7-iodo-8-hydroxy quinoline (5CL7I8HQ) have been investigated in details by means of spectroscopic characterization and computational molecular modelling techniques. FT-IR and FT-Raman experimental spectroscopic approaches have been utilized in order to obtain detailed spectroscopic signatures of title compounds, while DFT calculations have been used in order to visualize and assign vibrations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the title molecules exhibit NLO properties. The evaluated HOMO and LUMO energies demonstrate the chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyperconjugative interactions and charge delocalization. DFT calculations have been also used jointly with MD simulations in order to investigate in details global and local reactivity properties of title compounds. Also, molecular docking has been also used in order to investigate affinity of title compounds against decarboxylase inhibitor and quinoline derivatives can be a lead compounds for developing new antiparkinsonian drug.

Stabilization of axisymmetric liquid bridges through vibration-induced pressure fields.

Science.gov (United States)

Haynes, M; Vega, E J; Herrada, M A; Benilov, E S; Montanero, J M

2018-03-01

Previous theoretical studies have indicated that liquid bridges close to the Plateau-Rayleigh instability limit can be stabilized when the upper supporting disk vibrates at a very high frequency and with a very small amplitude. The major effect of the vibration-induced pressure field is to straighten the liquid bridge free surface to compensate for the deformation caused by gravity. As a consequence, the apparent Bond number decreases and the maximum liquid bridge length increases. In this paper, we show experimentally that this procedure can be used to stabilize millimeter liquid bridges in air under normal gravity conditions. The breakup of vibrated liquid bridges is examined experimentally and compared with that produced in absence of vibration. In addition, we analyze numerically the dynamics of axisymmetric liquid bridges far from the Plateau-Rayleigh instability limit by solving the Navier-Stokes equations. We calculate the eigenfrequencies characterizing the linear oscillation modes of vibrated liquid bridges, and determine their stability limits. The breakup process of a vibrated liquid bridge at that stability limit is simulated too. We find qualitative agreement between the numerical predictions for both the stability limits and the breakup process and their experimental counterparts. Finally, we show the applicability of our technique to control the amount of liquid transferred between two solid surfaces. Copyright © 2017 Elsevier Inc. All rights reserved.

Nature of infrared-active phonon sidebands to internal vibrations: Spectroscopic studies of solid oxygen and nitrogen

Science.gov (United States)

Brodyanski, A. P.; Medvedev, S. A.; Vetter, M.; Kreutz, J.; Jodl, H. J.

2002-09-01

The ir-active phonon sidebands to internal vibrations of oxygen and nitrogen were precisely investigated by Fourier transform infrared spectroscopy in the fundamental and first overtone spectral regions from 10 K to the boiling points at ambient pressure. We showed that an analysis of ir-active phonon sidebands yields important information on the internal vibrations of molecules in a condensed medium (solid or liquid), being complementary to Raman data on vibron frequencies. Analyzing the complete profile of these bands, we determined the band origin frequencies and explored their temperature behavior in all phases of both substances. We present unambiguous direct experimental proofs that this quality corresponds to the frequency of internal vibrations of single molecules. Considering solid oxygen and nitrogen as two limiting cases for simple molecular solids, we interpret this result as a strong evidence for a general fact that an ir-active phonon sideband possesses the same physical origin in pure molecular solids and in impurity centers. The key characteristics of the fundamental vibron energy zone (environmental and resonance frequency shifts) were deduced from the combined analysis of ir and Raman experimental data and their temperature behavior was explored in solid and liquid phases of oxygen and nitrogen at ambient pressure. The character of the short-range orientational order was established in the β-nitrogen based on our theoretical analysis consistent with the present experimental results. We also present the explanation of the origin of pressure-caused changes in the frequency of the Raman vibron mode of solid oxygen at low temperatures.

Studies of Heterogeneously Catalyzed Liquid-Phase Alcohol Oxidation on Platinum bySum-frequency Generation Vibrational Spectroscopy and Reaction Rate Measurements

Energy Technology Data Exchange (ETDEWEB)

Thompson, Christopher [Univ. of California, Berkeley, CA (United States)

2014-05-15

Compared to many branches of chemistry, the molecular level study of catalytically active surfaces is young. Only with the invention of ultrahigh vacuum technology in the past half century has it been possible to carry out experiments that yield useful molecular information about the reactive occurrences at a surface. The reason is two-fold: low pressure is necessary to keep a surface clean for an amount of time long enough to perform an experiment, and most atomic scale techniques that are surface speci c (x-ray photoelectron spectroscopy, electron energy loss spectroscopy, Auger electron spectroscopy, etc.) cannot be used at ambient pressures, because electrons, which act as chemical probes in these techniques, are easily scattered by molecules. Sum-frequency generation (SFG) vibrational spectroscopy is one technique that can provide molecular level information from the surface without the necessity for high vacuum. Since the advent of SFG as a surface spectroscopic tool it has proved its worth in the studies of surface catalyzed reactions in the gas phase, with numerous reactions in the gas phase having been investigated on a multitude of surfaces. However, in situ SFG characterization of catalysis at the solid-liquid interface has yet to be thoroughly pursued despite the broad interest in the use of heterogeneous catalysts in the liquid phase as replacements for homogeneous counterparts. This work describes an attempt to move in that direction, applying SFG to study the solid-liquid interface under conditions of catalytic alcohol oxidation on platinum.

Vibrational multiconfiguration self-consistent field theory: implementation and test calculations.

Science.gov (United States)

Heislbetz, Sandra; Rauhut, Guntram

2010-03-28

A state-specific vibrational multiconfiguration self-consistent field (VMCSCF) approach based on a multimode expansion of the potential energy surface is presented for the accurate calculation of anharmonic vibrational spectra. As a special case of this general approach vibrational complete active space self-consistent field calculations will be discussed. The latter method shows better convergence than the general VMCSCF approach and must be considered the preferred choice within the multiconfigurational framework. Benchmark calculations are provided for a small set of test molecules.

Study of the Internal Flow and Evaporation Characteristic Inside a Water Droplet on a Vertical Vibrating Hydrophobic Surface

Energy Technology Data Exchange (ETDEWEB)

Park, Chang-Seok; Lim, Hee-Chang [Pusan Nat’l Univ., Busan (Korea, Republic of)

2017-01-15

Thermal Marangoni flow has been observed inside droplets on heated surfaces, finally resulting in a coffee stain effect. This study aims to visualize and control the thermal Marangoni flow by employing periodic vertical vibration. The variations in the contact angle and internal volume of the droplet as it evaporates is observed by using a combination of continuous light and a still camera. With regard to the internal velocity, the particle image velocimetry system is applied to visualize the internal thermal Marangoni flow. In order to estimate the internal temperature gradient and surface tension on the surface of a droplet, the theoretical model based on the conduction and convection theory of heat transfer is applied. Thus, the internal velocity increases with an increase in plate temperature. The flow directions of the Marangoni and gravitational flows are opposite, and hence, it may be possible to control the coffee stain effect.

Spectroscopic techniques in the study of human tissues and their components. Part I: IR spectroscopy.

Science.gov (United States)

Olsztyńska-Janus, Sylwia; Szymborska-Małek, Katarzyna; Gąsior-Głogowska, Marlena; Walski, Tomasz; Komorowska, Małgorzata; Witkiewicz, Wojciech; Pezowicz, Celina; Kobielarz, Magdalena; Szotek, Sylwia

2012-01-01

Among the currently used methods of monitoring human tissues and their components many types of research are distinguished. These include spectroscopic techniques. The advantage of these techniques is the small amount of sample required, the rapid process of recording the spectra, and most importantly in the case of biological samples - preparation of tissues is not required. In this work, vibrational spectroscopy: ATR-FTIR and Raman spectroscopy will be used. Studies are carried out on tissues: tendons, blood vessels, skin, red blood cells and biological components: amino acids, proteins, DNA, plasma, and deposits.

Turbine blade vibration dampening

Science.gov (United States)

Cornelius, C.C.; Pytanowski, G.P.; Vendituoli, J.S.

1997-07-08

The present turbine wheel assembly increases component life and turbine engine longevity. The combination of the strap and the opening combined with the preestablished area of the outer surface of the opening and the preestablished area of the outer circumferential surface of the strap and the friction between the strap and the opening increases the life and longevity of the turbine wheel assembly. Furthermore, the mass ``M`` or combined mass ``CM`` of the strap or straps and the centrifugal force assist in controlling vibrations and damping characteristics. 5 figs.

A study of the flow boiling heat transfer in a minichannel for a heated wall with surface texture produced by vibration-assisted laser machining

International Nuclear Information System (INIS)

Piasecka, Magdalena; Strąk, Kinga; Grabas, Bogusław; Maciejewska, Beata

2016-01-01

The paper presents results concerning flow boiling heat transfer in a vertical minichannel with a depth of 1.7 mm and a width of 16 mm. The element responsible for heating FC-72, which flowed laminarly in the minichannel, was a plate with an enhanced surface. Two types of surface textures were considered. Both were produced by vibration-assisted laser machining. Infrared thermography was used to record changes in the temperature on the outer smooth side of the plate. Two-phase flow patterns were observed through a glass pane. The main aim of the study was to analyze how the two types of surface textures affect the heat transfer coefficient. A two-dimensional heat transfer approach was proposed to determine the local values of the heat transfer coefficient. The inverse problem for the heated wall was solved using a semi-analytical method based on the Trefftz functions. The results are presented as relationships between the heat transfer coefficient and the distance along the minichannel length and as boiling curves. The experimental data obtained for the two types of enhanced heated surfaces was compared with the results recorded for the smooth heated surface. The highest local values of the heat transfer coefficient were reported in the saturated boiling region for the plate with the type 1 texture produced by vibration-assisted laser machining. (paper)

A combined Raman spectroscopic and theoretical investigation of fundamental vibrational bands of furfuryl alcohol (2-furanmethanol)

DEFF Research Database (Denmark)

Barsberg, S.; Berg, Rolf W.

2006-01-01

. study of FA in weakly interacting environments. It is the first study of FA vibrational properties based on d. functional theory (DFT/B3LYP), and a recently proposed hybrid approach to the calcn. of fundamental frequencies, which also includes an anharmonic contribution. FA occupies five different...

Vibrational inelastic and charge transfer processes in H++H2 system: An ab initio study

Science.gov (United States)

Amaran, Saieswari; Kumar, Sanjay

2007-12-01

State-resolved differential cross sections, total and integral cross sections, average vibrational energy transfer, and the relative probabilities are computed for the H++H2 system using the newly obtained ab initio potential energy surfaces at the full CI/cc-pVQZ level of accuracy which allow for both the direct vibrational inelastic and the charge transfer processes. The quantum dynamics is treated within the vibrational close-coupling infinite-order-sudden approximation approach using the two ab initio quasidiabatic potential energy surfaces. The computed collision attributes for both the processes are compared with the available state-to-state scattering experiments at Ec.m.=20eV. The results are in overall good agreement with most of the observed scattering features such as rainbow positions, integral cross sections, and relative vibrational energy transfers. A comparison with the earlier theoretical study carried out on the semiempirical surfaces (diatomics in molecules) is also made to illustrate the reliability of the potential energy surfaces used in the present work.

Spectroscopic and antimicrobial studies of polystyrene films under ...

Indian Academy of Sciences (India)

Spectroscopic and antimicrobial studies of polystyrene films under air plasma and He-Ne laser treatment ... The parameters such as (1) surface area by contact angle measurements, (2) quality of material before and after treatment by SEM and FTIR spectra and (3) material characterization by UV-vis spectra were studied.

The vibrational Jahn–Teller effect in E⊗e systems

Energy Technology Data Exchange (ETDEWEB)

Thapaliya, Bishnu P.; Dawadi, Mahesh B.; Ziegler, Christopher; Perry, David S., E-mail: dperry@uakron.edu

2015-10-16

Highlights: • The vibrational Jahn–Teller effect is documented for three E⊗e molecular systems. • The spontaneous vibrational Jahn–Teller distortion is very small. • Vibrational Jahn–Teller splittings are substantial (1–60 cm{sup −1}). • Vibrational conical intersections in CH{sub 3}OH are accessible at low energies. - Abstract: The Jahn–Teller theorem is applied in the vibrational context where degenerate high-frequency vibrational states (E) are considered as adiabatic functions of low-frequency vibrational coordinates (e). For CH{sub 3}CN and Cr(C{sub 6}H{sub 6})(CO){sub 3}, the global minimum of the non-degenerate electronic potential energy surface occurs at the C{sub 3v} geometry, but in CH{sub 3}OH, the equilibrium geometry is far from the C{sub 3v} reference geometry. In the former cases, the computed spontaneous Jahn–Teller distortion is exceptionally small. In methanol, the vibrational Jahn–Teller interaction results in the splitting of the degenerate E-type CH stretch into what have been traditionally assigned as the distinct ν{sub 2} and ν{sub 9} vibrational bands. The ab initio vibrational frequencies are fit precisely by a two-state high-order Jahn–Teller Hamiltonian (Viel and Eisfeld, 2004). The presence of vibrational conical intersections, including 7 for CH{sub 3}OH, has implications for spectroscopy, for geometric phase, and for ultrafast localized non-adiabatic energy transfer.

A Combined Probe-Molecule, Mössbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst

Energy Technology Data Exchange (ETDEWEB)

Kneebone, Jared L. [Univ. of Rochester, Rochester, NY (United States); Daifuku, Stephanie L. [Univ. of Rochester, Rochester, NY (United States); Kehl, Jeffrey A. [Univ. of Rochester, Rochester, NY (United States); Wu, Gang [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Chung, Hoon T. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hu, Michael Y. [Argonne National Lab. (ANL), Argonne, IL (United States); Alp, E. Ercan [Argonne National Lab. (ANL), Argonne, IL (United States); More, Karren L. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Zelenay, Piotr [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Holby, Edward F. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Neidig, Michael L. [Univ. of Rochester, Rochester, NY (United States)

2017-07-06

While non-precious metal M-N-C (M = Fe or Co) catalysts have been developed that are effective for the oxygen reduction reaction in polymer electrolyte fuel cells, no consensus has yet been reached regarding the nature of the M sites in these heterogeneous catalysts that are responsible for reaction with dioxygen (O₂). While multiple studies have developed correlations between Fe distributions in as-prepared catalysts and ORR activity, the direct identification of sites reactive towards O₂ or O₂-analog molecules remains a significant challenge. In the present study, we demonstrate a new approach to identifying and characterizing potential Fe active sites in complex ORR catalysts that combines an effective probe molecule (NO_(g)) Mössbauer spectroscopy and nuclear resonance vibrational spectroscopy (NRVS) with density functional theory (DFT) calculations. Mössbauer spectroscopic studies demonstrate that NO_(g) treatment of electrochemically reduced PANI-57Fe-C leads to selective reaction with only a sub-set of the Fe species present. Nuclear resonance vibrational spectroscopic studies identified new Fe-ligand vibrations associated with the site reactive towards NO_(g). DFT calculations of vibrational properties of a small selection of previously proposed active site structures suggest that graphene zig-zag edge hosted Fe-N structures may be responsible for the observed vibrational behavior with NO_(g) probe molecules. Moreover, such sites are likely also reactive to O₂, possibly serving as the ORR active sites in the synthesized materials.

Evaluation of a vibration diagnostic system for the detection of spur gear pitting failures

Science.gov (United States)

Townsend, Dennis P.; Zakrajsek, James J.

1993-01-01

A vibration diagnostic system was used to detect spur gear surface pitting fatigue in a closed-loop spur gear fatigue test rig. The diagnostic system, comprising a personal computer with an analog-to-digital conversion board, a diagnostic system unit, and software, uses time-synchronous averaging of the vibration signal to produce a vibration image of each tooth on any gear in a transmission. Several parameters were analyzed including gear pair stress wave and raw baseband vibration, kurtosis, peak ratios, and others. The system provides limits for the various parameters and gives a warning when the limits are exceeded. Several spur gear tests were conducted with this system and vibration data analyzed at 5-min. intervals. The results presented herein show that the system is fairly effective at detecting spur gear tooth surface fatigue pitting failures.

Albumin adsorption on oxide thin films studied by spectroscopic ellipsometry

Energy Technology Data Exchange (ETDEWEB)

Silva-Bermudez, P., E-mail: suriel21@yahoo.com [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior s/n, C.U., 04510, Mexico D.F. (Mexico); Unidad de Posgrado, Facultad de Odontologia, Universidad Nacional Autonoma de Mexico, CU, 04510, Mexico D.F. (Mexico); Rodil, S.E.; Muhl, S. [Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Circuito Exterior s/n, C.U., 04510, Mexico D.F. (Mexico)

2011-12-15

Thin films of tantalum, niobium, zirconium and titanium oxides were deposited by reactive magnetron sputtering and their wettability and surface energy, optical properties, roughness, chemical composition and microstructure were characterized using contact angle measurements, spectroscopic ellipsometry, profilometry, X-ray photoelectron spectroscopy and X-ray diffraction, respectively. The purpose of the work was to correlate the surface properties of the films to the Bovine Serum Albumin (BSA) adsorption, as a first step into the development of an initial in vitro test of the films biocompatibility, based on standardized protein adsorption essays. The films were immersed into BSA solutions with different protein concentrations and protein adsorption was monitored in situ by dynamic ellipsometry; the adsorption-rate was dependent on the solution concentration and the immersion time. The overall BSA adsorption was studied in situ using spectroscopic ellipsometry and it was found to be influenced by the wettability of the films; larger BSA adsorption occurred on the more hydrophobic surface, the ZrO{sub 2} film. On the Ta{sub 2}O{sub 5}, Nb{sub 2}O{sub 5} and TiO{sub 2} films, hydrophilic surfaces, the overall BSA adsorption increased with the surface roughness or the polar component of the surface energy.

Quantum Monte Carlo for vibrating molecules

International Nuclear Information System (INIS)

Brown, W.R.; Lawrence Berkeley National Lab., CA

1996-08-01

Quantum Monte Carlo (QMC) has successfully computed the total electronic energies of atoms and molecules. The main goal of this work is to use correlation function quantum Monte Carlo (CFQMC) to compute the vibrational state energies of molecules given a potential energy surface (PES). In CFQMC, an ensemble of random walkers simulate the diffusion and branching processes of the imaginary-time time dependent Schroedinger equation in order to evaluate the matrix elements. The program QMCVIB was written to perform multi-state VMC and CFQMC calculations and employed for several calculations of the H 2 O and C 3 vibrational states, using 7 PES's, 3 trial wavefunction forms, two methods of non-linear basis function parameter optimization, and on both serial and parallel computers. In order to construct accurate trial wavefunctions different wavefunctions forms were required for H 2 O and C 3 . In order to construct accurate trial wavefunctions for C 3 , the non-linear parameters were optimized with respect to the sum of the energies of several low-lying vibrational states. In order to stabilize the statistical error estimates for C 3 the Monte Carlo data was collected into blocks. Accurate vibrational state energies were computed using both serial and parallel QMCVIB programs. Comparison of vibrational state energies computed from the three C 3 PES's suggested that a non-linear equilibrium geometry PES is the most accurate and that discrete potential representations may be used to conveniently determine vibrational state energies

Systematic studies of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher derivative methods: Applications to asymmetric and symmetric top and linear polyatomic molecules

International Nuclear Information System (INIS)

Clabo, D.A. Jr.

1987-04-01

Inclusion of the anharmonicity normal mode vibrations [i.e., the third and fourth (and higher) derivatives of a molecular Born-Oppenheimer potential energy surface] is necessary in order to theoretically reproduce experimental fundamental vibrational frequencies of a molecule. Although ab initio determinations of harmonic vibrational frequencies may give errors of only a few percent by the inclusion of electron correlation within a large basis set for small molecules, in general, molecular fundamental vibrational frequencies are more often available from high resolution vibration-rotation spectra. Recently developed analytic third derivatives methods for self-consistent-field (SCF) wavefunctions have made it possible to examine with previously unavailable accuracy and computational efficiency the anharmonic force fields of small molecules

Systematic studies of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher derivative methods: Applications to asymmetric and symmetric top and linear polyatomic molecules

Energy Technology Data Exchange (ETDEWEB)

Clabo, D.A. Jr.

1987-04-01

Inclusion of the anharmonicity normal mode vibrations (i.e., the third and fourth (and higher) derivatives of a molecular Born-Oppenheimer potential energy surface) is necessary in order to theoretically reproduce experimental fundamental vibrational frequencies of a molecule. Although ab initio determinations of harmonic vibrational frequencies may give errors of only a few percent by the inclusion of electron correlation within a large basis set for small molecules, in general, molecular fundamental vibrational frequencies are more often available from high resolution vibration-rotation spectra. Recently developed analytic third derivatives methods for self-consistent-field (SCF) wavefunctions have made it possible to examine with previously unavailable accuracy and computational efficiency the anharmonic force fields of small molecules.

Contribution of Adsorbed Protein Films to Nanoscopic Vibrations Exhibited by Bacteria Adhering through Ligand-Receptor Bonds

NARCIS (Netherlands)

Song, Lei; Sjollema, Jelmer; Norde, Willem; Busscher, Henk J.; van der Mei, Henny C.

2015-01-01

Bacteria adhering to surfaces exhibit nanoscopic vibrations that depend on the viscoelasticity of the bond. The quantification of the nanoscopic vibrations of bacteria adhering to surfaces provides new opportunities to better understand the properties of the bond through which bacteria adhere and

Vibrationally Assisted Electron Transfer Mechanism of Olfaction: Myth or Reality?

DEFF Research Database (Denmark)

Solov'yov, Ilia; Chang, Po-Yao; Schulten, Klaus

2012-01-01

to this suggestion an olfactory receptor is activated by electron transfer assisted through odorant vibrational excitation. The hundreds to thousands of different olfactory receptors in an animal recognize odorants over a discriminant landscape with surface properties and vibrational frequencies as the two major...... dimensions. In the present paper we introduce the vibrationally assisted mechanism of olfaction and demonstrate for several odorants that, indeed, a strong enhancement of an electron tunneling rate due to odorant vibrations can arise. We discuss in this regard the influence of odorant deuteration and explain...... olfactory receptors and odorants must obey for the vibrationally assisted electron transfer mechanism to function. We argue that the stated characteristics are feasible for realistic olfactory receptors, noting, though, that the receptor structure presently is still unknown, but can be studied through...

Selective probe of the morphology and local vibrations at carbon nanoasperities

Energy Technology Data Exchange (ETDEWEB)

Fujimori, Toshihiko; Endo, Morinobu; Kaneko, Katsumi [Research Center for Exotic Nanocarbons (JST), Shinshu University, 4-17-1, Wakasato, Nagano-city 380-8553 (Japan); Urita, Koki; Moriguchi, Isamu [Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, 1-14 Bunkyo-machi, Nagasaki-shi, Nagasaki 852-8521 (Japan); Tomanek, David [Physics and Astronomy Department, Michigan State University, East Lansing, Michigan 48824 (United States); Ohba, Tomonori [Department of Chemistry, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522 (Japan)

2012-02-14

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm{sup -1}, which are obscured in regular Raman spectra. Ab initio density functional calculations assign modes in this frequency range to local vibrations at the nanohorn cap resembling the radial breathing mode of fullerenes. Careful interpretation of our SERS spectra indicates presence of caps with 5 or 6 pentagons, which are chemically the most active sites. Changes in the peak intensities and frequencies with time indicate that exposure to laser irradiation may cause structural rearrangements at the cap.

Vocal fold contact patterns based on normal modes of vibration.

Science.gov (United States)

Smith, Simeon L; Titze, Ingo R

2018-05-17

The fluid-structure interaction and energy transfer from respiratory airflow to self-sustained vocal fold oscillation continues to be a topic of interest in vocal fold research. Vocal fold vibration is driven by pressures on the vocal fold surface, which are determined by the shape of the glottis and the contact between vocal folds. Characterization of three-dimensional glottal shapes and contact patterns can lead to increased understanding of normal and abnormal physiology of the voice, as well as to development of improved vocal fold models, but a large inventory of shapes has not been directly studied previously. This study aimed to take an initial step toward characterizing vocal fold contact patterns systematically. Vocal fold motion and contact was modeled based on normal mode vibration, as it has been shown that vocal fold vibration can be almost entirely described by only the few lowest order vibrational modes. Symmetric and asymmetric combinations of the four lowest normal modes of vibration were superimposed on left and right vocal fold medial surfaces, for each of three prephonatory glottal configurations, according to a surface wave approach. Contact patterns were generated from the interaction of modal shapes at 16 normalized phases during the vibratory cycle. Eight major contact patterns were identified and characterized by the shape of the flow channel, with the following descriptors assigned: convergent, divergent, convergent-divergent, uniform, split, merged, island, and multichannel. Each of the contact patterns and its variation are described, and future work and applications are discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

The importance of accurate adiabatic interaction potentials for the correct description of electronically nonadiabatic vibrational energy transfer: A combined experimental and theoretical study of NO(v = 3) collisions with a Au(111) surface

Energy Technology Data Exchange (ETDEWEB)

Golibrzuch, Kai; Shirhatti, Pranav R.; Kandratsenka, Alexander; Wodtke, Alec M.; Bartels, Christof [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Rahinov, Igor [Department of Natural Sciences, The Open University of Israel, Ra' anana 4353701 (Israel); Auerbach, Daniel J. [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106 (United States)

2014-01-28

We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam–surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.

Nonlinear vibration of double-walled boron nitride and carbon nanopeapods under multi-physical fields with consideration of surface stress effects

Science.gov (United States)

Ghorbanpour Arani, A.; Sabzeali, M.; BabaAkbar Zarei, H.

2017-12-01

In this study, the nonlinear thermo-electro vibrations of double-walled boron nitride nanopeapods (DWBNNPPs) and double-walled carbon nanopeapods (DWCNPPs) under magnetic field embedded in an elastic medium is investigated. DWBNNPPs are made of piezoelectric and smart materials therefore, electric field is effective on them; meanwhile, DWCNPPs are made of carbon thus, magnetic field can be useful to control them. The Pasternak model is used to simulate the effects of elastic medium which surrounds the system. Nanotubes are modeled with assumption of the Euler-Bernoulli beam (EBB) theory and the surface effects are considered to achieve accurate response of the system. Moreover, interaction between two layers is modeled by van der Waals (vdW) forces. The equations of motion are derived using the energy method and the Hamilton principle. Then the governing equations are solved by using Galerkin's method and incremental harmonic balance method (IHBM). The influences of various parameters such as the magnetic field, different types of DWCNPPs and DWBNNPPs, elastic medium, existence of fullerene and surface effect on the vibration behavior of the system are investigated. The results demonstrate that DWBNNPPs have more influence on the frequency of the system than DWCNPPs. In addition, the presence of fullerene in nanotubes has a negative impact on the frequency behavior of revisionthe system.

Environmental vibration reduction utilizing an array of mass scatterers

DEFF Research Database (Denmark)

Peplow, Andrew; Andersen, Lars Vabbersgaard; Bucinskas, Paulius

2017-01-01

.g. concrete or stone blocks, specially designed brick walls, etc.). The natural frequencies of vibration for such blocks depend on the local ground stiffness and on the mass of the blocks which can be chosen to provide resonance at specified frequencies. This work concerns the effectiveness of such “blocking......Ground vibration generated by rail and road traffic is a major source of environmental noise and vibration pollution in the low-frequency range. A promising and cost effective mitigation method can be the use of heavy masses placed as a periodic array on the ground surface near the road or track (e...

Characterization of the Elusive Conformers of Glycine from State-of-the-Art Structural, Thermodynamic, and Spectroscopic Computations: Theory Complements Experiment.

Science.gov (United States)

Barone, Vincenzo; Biczysko, Malgorzata; Bloino, Julien; Puzzarini, Cristina

2013-03-12

A state-of-the-art computational strategy for the evaluation of accurate molecular structures as well as thermodynamic and spectroscopic properties along with the direct simulation of infrared (IR) and Raman spectra is established, validated (on the basis of the experimental data available for the Ip glycine conformer) and then used to provide a reliable and accurate characterization of the elusive IVn/gtt and IIIp/tct glycine conformers. The integrated theoretical model proposed is based on accurate post-Hartree-Fock computations (involving composite schemes) of energies, structures, properties, and harmonic force fields coupled to DFT corrections for the proper inclusion of vibrational effects at an anharmonic level (as provided by general second-order perturbative approach). It is shown that the approach presented here allows the evaluation of structural, thermodynamic, and spectroscopic properties with an overall accuracy of about, or better than, 0.001 Å, 20 MHz, 1 kJ·mol(-1), and 10 cm(-1) for bond distances, rotational constants, conformational enthalpies, and vibrational frequencies, respectively. The high accuracy of the computational results allows one to support and complement experimental studies, thus providing (i) an unequivocal identification of several conformers concomitantly present in the experimental mixture and (ii) data not available or difficult to experimentally derive.

Conditions for Stable Chip Breaking and Provision of Machined Surface Quality While Turning with Asymmetric Tool Vibrations

OpenAIRE

Шелег, В. К.; Молочко, В. И.; Данильчик, С. С.

2015-01-01

The paper considers a process of turning structural steel with asymmetric tool vibrations directed along feeding. Asymmetric vibrations characterized by asymmetry coefficient of vibration cycle, their frequency and amplitude are additionally transferred to the tool in the turning process with the purpose to crush chips. Conditions of stable chip breaking and obtaining optimum dimensions of chip elements have been determined in the paper. In order to reduce a negative impact of the vibration a...

MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO⁺(H₂O) cluster using accurate potential energy and dipole moment surfaces.

Science.gov (United States)

Homayoon, Zahra

2014-09-28

A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO(+)(H2O) cluster is reported. The PES is based on fitting of roughly 32,000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO(+)(H2O) and NO(+)(D2O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO(+)(H2O) and NO(+)(D2O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO(+)(H2O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water "antisymmetric" stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO+(H2O) cluster using accurate potential energy and dipole moment surfaces

Science.gov (United States)

Homayoon, Zahra

2014-09-01

A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO+(H2O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO+(H2O) and NO+(D2O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO+(H2O) and NO+(D2O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO+(H2O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water "antisymmetric" stretching mode with the low-frequency intermolecular modes results in intensity borrowing.

MULTIMODE quantum calculations of vibrational energies and IR spectrum of the NO+(H2O) cluster using accurate potential energy and dipole moment surfaces

International Nuclear Information System (INIS)

Homayoon, Zahra

2014-01-01

A new, full (nine)-dimensional potential energy surface and dipole moment surface to describe the NO + (H 2 O) cluster is reported. The PES is based on fitting of roughly 32 000 CCSD(T)-F12/aug-cc-pVTZ electronic energies. The surface is a linear least-squares fit using a permutationally invariant basis with Morse-type variables. The PES is used in a Diffusion Monte Carlo study of the zero-point energy and wavefunction of the NO + (H 2 O) and NO + (D 2 O) complexes. Using the calculated ZPE the dissociation energies of the clusters are reported. Vibrational configuration interaction calculations of NO + (H 2 O) and NO + (D 2 O) using the MULTIMODE program are performed. The fundamental, a number of overtone, and combination states of the clusters are reported. The IR spectrum of the NO + (H 2 O) cluster is calculated using 4, 5, 7, and 8 modes VSCF/CI calculations. The anharmonic, coupled vibrational calculations, and IR spectrum show very good agreement with experiment. Mode coupling of the water “antisymmetric” stretching mode with the low-frequency intermolecular modes results in intensity borrowing

Advancing the Frontiers in Nanocatalysis, Biointerfaces, and Renewable Energy Conversion by Innovations of Surface Techniques

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.; Frei, H.; Park, J.Y.

2009-07-23

The challenge of chemistry in the 21st century is to achieve 100% selectivity of the desired product molecule in multipath reactions ('green chemistry') and develop renewable energy based processes. Surface chemistry and catalysis play key roles in this enterprise. Development of in situ surface techniques such as high-pressure scanning tunneling microscopy, sum frequency generation (SFG) vibrational spectroscopy, time-resolved Fourier transform infrared methods, and ambient pressure X-ray photoelectron spectroscopy enabled the rapid advancement of three fields: nanocatalysts, biointerfaces, and renewable energy conversion chemistry. In materials nanoscience, synthetic methods have been developed to produce monodisperse metal and oxide nanoparticles (NPs) in the 0.8-10 nm range with controlled shape, oxidation states, and composition; these NPs can be used as selective catalysts since chemical selectivity appears to be dependent on all of these experimental parameters. New spectroscopic and microscopic techniques have been developed that operate under reaction conditions and reveal the dynamic change of molecular structure of catalysts and adsorbed molecules as the reactions proceed with changes in reaction intermediates, catalyst composition, and oxidation states. SFG vibrational spectroscopy detects amino acids, peptides, and proteins adsorbed at hydrophobic and hydrophilic interfaces and monitors the change of surface structure and interactions with coadsorbed water. Exothermic reactions and photons generate hot electrons in metal NPs that may be utilized in chemical energy conversion. The photosplitting of water and carbon dioxide, an important research direction in renewable energy conversion, is discussed.

A Single Chiroptical Spectroscopic Method May Not Be Able To Establish the Absolute Configurations of Diastereomers: Dimethylesters of Hibiscus and Garcinia Acids

Science.gov (United States)

Polavarapu, Prasad L.; Donahue, Emily A.; Shanmugam, Ganesh; Scalmani, Giovanni; Hawkins, Edward K.; Rizzo, Carmelo; Ibnusaud, Ibrahim; Thomas, Grace; Habel, Deenamma; Sebastian, Dellamol

2013-01-01

Electronic circular dichroism (ECD), optical rotatory dispersion (ORD), and vibrational circular dichroism (VCD) spectra of hibiscus acid dimethyl ester have been measured and analyzed in combination with quantum chemical calculations of corresponding spectra. These results, along with those reported previously for garcinia acid dimethyl ester, reveal that none of these three (ECD, ORD, or VCD) spectroscopic methods, in isolation, can unequivocally establish the absolute configurations of diastereomers. This deficiency is eliminated when a combined spectral analysis of either ECD and VCD or ORD and VCD methods is used. It is also found that the ambiguities in the assignment of absolute configurations of diastereomers may also be overcome when unpolarized vibrational absorption is included in the spectral analysis. PMID:21568330

Anharmonic vibrational properties in periodic systems: energy, electron-phonon coupling, and stress

OpenAIRE

Monserrat, Bartomeu; Drummond, N. D.; Needs, R. J.

2013-01-01

A unified approach is used to study vibrational properties of periodic systems with first-principles methods and including anharmonic effects. Our approach provides a theoretical basis for the determination of phonon-dependent quantities at finite temperatures. The low-energy portion of the Born-Oppenheimer energy surface is mapped and used to calculate the total vibrational energy including anharmonic effects, electron-phonon coupling, and the vibrational contribution to the stress tensor. W...

[Occupational standing vibration rate and vibrational diseases].

Science.gov (United States)

Karnaukh, N G; Vyshchipan, V F; Haumenko, B S

2003-12-01

Occupational standing vibration rate is proposed in evaluating a degree of impairment of an organism activity. It will allow more widely to introduce specification of quality and quantity in assessment of the development of vibrational disease. According out-patient and inpatient obtained data we have established criterial values of functional changes in accordance with accumulated occupational standing vibration rate. The nomogram was worked out for defining a risk of the development of vibrational disease in mine workers. This nomogram more objectively can help in diagnostics of the disease.

Comparative studies of perceived vibration strength for commercial mobile phones.

Science.gov (United States)

Lee, Heow Pueh; Lim, Siak Piang

2014-05-01

A mobile phone, also known as cell phone or hand phone, is among the most popular electrical devices used by people all over the world. The present study examines the vibration perception of mobile phones by co-relating the relevant design parameters such as excitation frequency, and size and mass of mobile phones to the vibration perception survey by volunteers. Five popular commercially available mobile phone models were tested. The main findings for the perception surveys were that higher vibration frequency and amplitude of the peak acceleration would result in stronger vibration perception of the mobile phones. A larger contact surface area with the palms and figures, higher peak acceleration and the associated larger peak inertia force may be the main factors for the relatively higher vibration perception. The future design for the vibration alert of the mobile phones is likely to follow this trend. Copyright © 2013 Elsevier Ltd and The Ergonomics Society. All rights reserved.

Isotope separation using vibrationally excited molecules

International Nuclear Information System (INIS)

Woodroffe, J.A.; Keck, J.C.

1977-01-01

A system for isotope separation or enrichment wherein molecules of a selected isotope type in a flow of molecules of plural isotope types are vibrationally excited and collided with a background gas to provide enhanced diffusivity for the molecules of the selected isotope type permitting their separate collection. The system typically is for the enrichment of uranium using a uranium hexafluoride gas in combination with a noble gas such as argon. The uranium hexafluoride molecules having a specific isotope of uranium are vibrationally excited by laser radiation. The vibrational energy is converted to a translation energy upon collision with a particle of the background gas and the added translation energy enhances the diffusivity of the selected hexafluoride molecules facilitating its condensation on collection surfaces provided for that purpose. This process is periodically interrupted and the cryogenic flow halted to permit evaporation of the collected molecules to provide a distinct, enriched flow

Raman and terahertz spectroscopical investigation of cocrystal formation process of piracetam and 3-hydroxybenzoic acid

Science.gov (United States)

Du, Yong; Zhang, Huili; Xue, Jiadan; Fang, Hongxia; Zhang, Qi; Xia, Yi; Li, Yafang; Hong, Zhi

2015-03-01

Cocrystallization can improve physical and chemical properties of active pharmaceutical ingredient, and this feature has great potential in pharmaceutical development. In this study, the cocrystal of piracetam and 3-hydroxybenzoic acid under grinding condition has been characterized by Raman and terahertz spectroscopical techniques. The major vibrational modes of individual starting components and cocrystal are obtained and assigned. Spectral results show that the vibrational modes of the cocrystal are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman and THz spectra. The formation rate is pretty fast in first several 20 min grinding time, and then it becomes slow. After ∼35 min, such process has been almost completed. These results offer us the unique means and benchmark for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic during cocrystal formation process in pharmaceutical fields.

Behavior of Cell on Vibrating Micro Ridges

Directory of Open Access Journals (Sweden)

Haruka Hino

2015-06-01

Full Text Available The effect of micro ridges on cells cultured at a vibrating scaffold has been studied in vitro. Several parallel lines of micro ridges have been made on a disk of transparent polydimethylsiloxane for a scaffold. To apply the vibration on the cultured cells, a piezoelectric element was attached on the outside surface of the bottom of the scaffold. The piezoelectric element was vibrated by the sinusoidal alternating voltage (Vp-p < 16 V at 1.0 MHz generated by a function generator. Four kinds of cells were used in the test: L929 (fibroblast connective tissue of C3H mouse, Hepa1-6 (mouse hepatoma, C2C12 (mouse myoblast, 3T3-L1 (mouse fat precursor cells. The cells were seeded on the micro pattern at the density of 2000 cells/cm2 in the medium containing 10% FBS (fetal bovine serum and 1% penicillin/ streptomycin. After the adhesion of cells in several hours, the cells are exposed to the ultrasonic vibration for several hours. The cells were observed with a phase contrast microscope. The experimental results show that the cells adhere, deform and migrate on the scaffold with micro patterns regardless of the ultrasonic vibration. The effects of the vibration and the micro pattern depend on the kind of cells.

A Raman spectroscopic study of thermally treated glushinskite--the natural magnesium oxalate dihydrate.

Science.gov (United States)

Frost, Ray L; Adebajo, Moses; Weier, Matt L

2004-02-01

Raman spectroscopy has been used to study the thermal transformations of natural magnesium oxalate dihydrate known in mineralogy as glushinskite. The data obtained by Raman spectroscopy was supplemented with that of infrared emission spectroscopy. The vibrational spectroscopic data was complimented with high resolution thermogravimetric analysis combined with evolved gas mass spectrometry. TG-MS identified two mass loss steps at 146 and 397 degrees C. In the first mass loss step water is evolved only, in the second step carbon dioxide is evolved. The combination of Raman microscopy and a thermal stage clearly identifies the changes in the molecular structure with thermal treatment. Glushinskite is the dihydrate phase in the temperature range up to the pre-dehydration temperature of 146 degrees C. Above 397 degrees C, magnesium oxide is formed. Infrared emission spectroscopy shows that this mineral decomposes at around 400 degrees C. Changes in the position and intensity of the CO and CC stretching vibrations in the Raman spectra indicate the temperature range at which these phase changes occur.

Quantum Mechanical Determination of Potential Energy Surfaces for TiO and H2O

Science.gov (United States)

Langhoff, Stephen R.

1996-01-01

We discuss current ab initio methods for determining potential energy surfaces, in relation to the TiO and H2O molecules, both of which make important contributions to the opacity of oxygen-rich stars. For the TiO molecule we discuss the determination of the radiative lifetimes of the excited states and band oscillator strengths for both the triplet and singlet band systems. While the theoretical radiative lifetimes for TiO agree well with recent measurements, the band oscillator strengths differ significantly from those currently employed in opacity calculations. For the H2O molecule we discuss the current results for the potential energy and dipole moment ground state surfaces generated at NASA Ames. We show that it is necessary to account for such effects as core-valence Correlation energy to generate a PES of near spectroscopic accuracy. We also describe how we solve the ro-vibrational problem to obtain the line positions and intensities that are needed for opacity sampling.

Vibrational spectroscopic (FT-IR, FT-Raman) and quantum mechanical study of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno[3,2-f] [1,2,4]triazolo[4,3-a][1,4] diazepine

Science.gov (United States)

Kuruvilla, Tintu K.; Prasana, Johanan Christian; Muthu, S.; George, Jacob

2018-04-01

The spectroscopic properties of 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine were investigated in the present study using FT-IR and FT-Raman techniques. The results obtained were compared with quantum mechanical methods, as it serves as an important tool in interpreting and predicting vibrational spectra. The optimized molecular geometry, the vibrational wavenumbers, the infrared intensities and Raman scattering were calculated using density functional theory B3LYP method with 6-311++g (d,p) basis set. All the experimental results were in line with the theoretical data. The molecular electrostatic potential (MEP) and HOMO LUMO energies of the title compound were accounted. The results indicated that the title compound has a lower softness value (0.27) and high electrophilicity index (4.98) hence describing its biological activity. Further, natural bond orbital was also analyzed as part of the work. Fukui functions were calculated in order to explain the chemical selectivity or the reactivity site in 4-(2-chlorophenyl)-2-ethyl-9-methyl-6H-thieno [3,2-f] [1,2,4] triazolo [4,3-a] [1,4] diazepine. The thermodynamic properties of the title compound were closely examined at different temperatures. It revealed the correlations between heat capacity (C), entropy (S) and enthalpy changes (H) with temperatures. The paper further explains that the title compound can act as good antidepressant through molecular docking studies.

Potential energy curves and spectroscopic properties of X2Σ+ and A2Π states of 13C14N

International Nuclear Information System (INIS)

Liao Jian-Wen; Yang Chuan-Lu

2014-01-01

The potential energy curves (PECs) of X 2 Σ + and A 2 Π states of the CN molecule have been calculated with the multi-reference configuration interaction method and the aug-cc-pwCV5Z basis set. Based on the PECs, all of the vibrational and rotational levels of the 13 C 14 N molecule are obtained by solving the Schrödinger equation of the molecular nuclear motion. The spectroscopic parameters are determined by fitting the Dunham coefficients with the levels. Both the levels and the spectroscopic parameters are in good qualitative agreement with the experimental data available. The analytical potential energy functions are also deduced from the calculated PECs. The present results can provide a helpful reference for future spectroscopy experiments or dynamical calculations of the molecule. (atomic and molecular physics)

Reduction method for residual stress of welded joint using random vibration

International Nuclear Information System (INIS)

Aoki, Shigeru; Nishimura, Tadashi; Hiroi, Tetsumaro

2005-01-01

Welded joints are used for construction of many structures. Residual stress is induced near the bead caused by locally given heat. Tensile residual stress on the surface may reduce fatigue strength. In this paper, a new method for reduction of residual stress using vibration during welding is proposed. As vibrational load, random vibration, white noise and filtered white noise are used. Two thin plates are butt-welded. Residual stress is measured with a paralleled beam X-ray diffractometer with scintillation counter after removing quenched scale chemically. It is concluded that tensile residual stress near the bead is reduced by using random vibration during welding

Surface atomic relaxation and magnetism on hydrogen-adsorbed Fe(110) surfaces from first principles

Energy Technology Data Exchange (ETDEWEB)

Chohan, Urslaan K.; Jimenez-Melero, Enrique [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Dalton Cumbrian Facility, The University of Manchester, Moor Row CA24 3HA (United Kingdom); Koehler, Sven P.K., E-mail: sven.koehler@manchester.ac.uk [Dalton Cumbrian Facility, The University of Manchester, Moor Row CA24 3HA (United Kingdom); School of Chemistry, The University of Manchester, Manchester M13 9PL (United Kingdom); Photon Science Institute, The University of Manchester, Manchester M13 9PL (United Kingdom)

2016-11-30

Highlights: • Potential energy surfaces for H diffusion on Fe(110) calculated. • Full vibrational analysis of surface modes performed. • Vibrational analysis establishes lb site as a transition state to the 3f site. • Pronounced buckling observed in the Fe surface layer. - Abstract: We have computed adsorption energies, vibrational frequencies, surface relaxation and buckling for hydrogen adsorbed on a body-centred-cubic Fe(110) surface as a function of the degree of H coverage. This adsorption system is important in a variety of technological processes such as the hydrogen embrittlement in ferritic steels, which motivated this work, and the Haber–Bosch process. We employed spin-polarised density functional theory to optimise geometries of a six-layer Fe slab, followed by frozen mode finite displacement phonon calculations to compute Fe–H vibrational frequencies. We have found that the quasi-threefold (3f) site is the most stable adsorption site, with adsorption energies of ∼3.0 eV/H for all coverages studied. The long-bridge (lb) site, which is close in energy to the 3f site, is actually a transition state leading to the stable 3f site. The calculated harmonic vibrational frequencies collectively span from 730 to 1220 cm{sup −1}, for a range of coverages. The increased first-to-second layer spacing in the presence of adsorbed hydrogen, and the pronounced buckling observed in the Fe surface layer, may facilitate the diffusion of hydrogen atoms into the bulk, and therefore impact the early stages of hydrogen embrittlement in steels.