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Sample records for combined pulsed-q dissociation

  1. Identification of Proteins and Phosphoproteins Using Pulsed Q Collision Induced Dissociation (PQD)

    NASA Astrophysics Data System (ADS)

    Wu, Wells W.; Wang, Guanghui; Insel, Paul A.; Hsiao, Cheng-Te; Zou, Sige; Maudsley, Stuart; Martin, Bronwen; Shen, Rong-Fong

    2011-10-01

    Pulsed Q collision induced dissociation (PQD) was developed to facilitate detection of low-mass reporter ions from labeling reagents (e.g., iTRΑQ) in peptide quantification using an LTQ mass spectrometer (MS). Despite the large number of linear ion traps worldwide, the use and optimization of PQD for protein identification have been limited, in part due to less effective ion fragmentation relative to the collision induced dissociation (CID). PQD expands the m/z coverage of fragment ions to the lower m/z range by circumventing the typical low mass cut-off of an ion trap MS. Since database searching relies on the matching between theoretical and observed spectra, it is not clear how ion intensity and peak number might affect the outcomes of a database search. In this report, we systematically evaluated the attributes of PQD mass spectra, performed intensity optimization, and assessed the benefits of using PQD on the identification of peptides and phosphopeptides from an LTQ. Based on head-to-head comparisons between CID (higher intensity) and PQD (better m/z coverage), peptides identified using PQD generally have Xcorr scores lower than those using CID. Such score differences were considerably diminished by the use of 0.1% m-nitrobenzyl alcohol (m-NBA) in mobile phases. The ion intensities of both CID and PQD were adversely affected by increasing m/z of the precursor, with PQD more sensitive than CID. In addition to negating the 1/3 rule, PQD enhances direct bond cleavage and generates patterns of fragment ions different from those of CID, particularly for peptides with a labile functional group (e.g., phosphopeptides). The higher energy fragmentation pathway of PQD on peptide fragmentation was further compared to those of CID and the quadrupole-type activation in parallel experiments.

  2. Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization.

    PubMed

    Halim, Mohammad A; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-09-01

    Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C-Cα backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C-N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization. Graphical Abstract ᅟ. PMID:27287047

  3. Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-06-01

    Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C-Cα backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C-N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization.

  4. Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization

    NASA Astrophysics Data System (ADS)

    Halim, Mohammad A.; Girod, Marion; MacAleese, Luke; Lemoine, Jérôme; Antoine, Rodolphe; Dugourd, Philippe

    2016-09-01

    Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C-Cα backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C-N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization.

  5. A combination thermal dissociation/electron impact ionization source for RIB generation

    SciTech Connect

    Alton, G.D.; Cui, B.; Welton, R.F.

    1996-12-31

    The flourishing interest in radioactive ion beams (RIBs) with intensities adequate for astrophysics and nuclear physics research place a premium on targets that will swiftly release trace amounts of short lived radio-nuclei in the presence of bulk quantities of target material and ion sources that have the capability of efficiently ionizing the release products. Because of the low probability of simultaneously dissociating and efficiently ionizing the individual atomic constituents of molecules containing the element of interest with conventional, hot-cathode, electron-impact ion sources, the species of interest is often distributed in several mass channels in the form of molecular sideband beams and, consequently, the intensity is diluted. The authors have conceived an ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high efficiency characteristics of an electron impact ionization source to address these problems. If the concept proves to be a viable option, the source will be used as a complement to the electron beam plasma ion sources already in use at the HRIBF. The design features and principles of operation of the source are described in this article.

  6. Combined infrared multiphoton dissociation and electron-capture dissociation using co-linear and overlapping beams in Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Mihalca, Romulus; van der Burgt, Yuri E M; McDonnell, Liam A; Duursma, Marc; Cerjak, Iliya; Heck, Albert J R; Heeren, Ron M A

    2006-01-01

    A novel set-up for Fourier transform ion cyclotron resonance mass spectrometry (FTICR) is reported for simultaneous infrared multiphoton dissociation (IRMPD) and electron-capture dissociation (ECD). An unmodified electron gun ensures complete, on-axis overlap between the electron and the photon beams. The instrumentation, design and implementation of this novel approach are described. In this configuration the IR beam is directed into the ICR cell using a pneumatically actuated mirror inserted into the ion-optical path. Concept validation was made using different combinations of IRMPD and ECD irradiation events on two standard peptides. The ability to perform efficient IRMPD, ECD and especially simultaneous IRMPD and ECD using lower irradiation times is demonstrated. The increase in primary sequence coverage, with the combined IRMPD and ECD set-up, also increases the confidence in peptide and protein assignments. PMID:16705647

  7. Combined impact of entropy and carrier delocalization on charge transfer exciton dissociation at the donor-acceptor interface

    NASA Astrophysics Data System (ADS)

    Ono, Shota; Ohno, Kaoru

    2016-08-01

    Several models of the charge transfer exciton (CTE) have been proposed to explain its dissociation at the donor-acceptor (DA) interface. However, the underlying physics is still under debate. Here, we derive a temperature (T ) dependent tight-binding model for an electron-hole pair at the DA interface. The main finding is the existence of the localization-delocalization transition at a critical T , which can explain the CTE dissociation. The present study highlights the combined effect of entropy (finite T ) and carrier delocalization in the CTE dissociation.

  8. Combined compared to dissociated oral and intestinal sucrose stimuli induce different brain hedonic processes

    PubMed Central

    Clouard, Caroline; Meunier-Salaün, Marie-Christine; Meurice, Paul; Malbert, Charles-Henri; Val-Laillet, David

    2014-01-01

    The characterization of brain networks contributing to the processing of oral and/or intestinal sugar signals in a relevant animal model might help to understand the neural mechanisms related to the control of food intake in humans and suggest potential causes for impaired eating behaviors. This study aimed at comparing the brain responses triggered by oral and/or intestinal sucrose sensing in pigs. Seven animals underwent brain single photon emission computed tomography (99mTc-HMPAO) further to oral stimulation with neutral or sucrose artificial saliva paired with saline or sucrose infusion in the duodenum, the proximal part of the intestine. Oral and/or duodenal sucrose sensing induced differential cerebral blood flow changes in brain regions known to be involved in memory, reward processes and hedonic (i.e., pleasure) evaluation of sensory stimuli, including the dorsal striatum, prefrontal cortex, cingulate cortex, insular cortex, hippocampus, and parahippocampal cortex. Sucrose duodenal infusion only and combined sucrose stimulation induced similar activity patterns in the putamen, ventral anterior cingulate cortex and hippocampus. Some brain deactivations in the prefrontal and insular cortices were only detected in the presence of oral sucrose stimulation. Finally, activation of the right insular cortex was only induced by combined oral and duodenal sucrose stimulation, while specific activity patterns were detected in the hippocampus and parahippocampal cortex with oral sucrose dissociated from caloric load. This study sheds new light on the brain hedonic responses to sugar and has potential implications to unravel the neuropsychological mechanisms underlying food pleasure and motivation. PMID:25147536

  9. Combined infrared multiphoton dissociation and electron capture dissociation with a hollow electron beam in Fourier transform ion cyclotron resonance mass spectrometry.

    PubMed

    Tsybin, Youri O; Witt, Matthias; Baykut, Gökhan; Kjeldsen, Frank; Håkansson, Per

    2003-01-01

    An electron injection system based on an indirectly heated ring-shaped dispenser cathode has been developed and installed in a 7 Tesla Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. This new hardware design allows high-rate electron capture dissociation (ECD) to be carried out by a hollow electron beam coaxial with the ion cyclotron resonance (ICR) trap. Infrared multiphoton dissociation (IRMPD) can also be performed with an on-axis IR-laser beam passing through a hole at the centre of the dispenser cathode. Electron and photon irradiation times of the order of 100 ms are required for efficient ECD and IRMPD, respectively. As ECD and IRMPD generate fragments of different types (mostly c, z and b, y, respectively), complementary structural information that improves the characterization of peptides and proteins by FTICR mass spectrometry can be obtained. The developed technique enables the consecutive or simultaneous use of the ECD and IRMPD methods within a single FTICR experimental sequence and on the same ensemble of trapped ions in multistage tandem (MS/MS/MS or MS(n)) mass spectrometry. Flexible changing between ECD and IRMPD should present advantages for the analysis of protein digests separated by liquid chromatography prior to FTICRMS. Furthermore, ion activation by either electron or laser irradiation prior to, as well as after, dissociation by IRMPD or ECD increases the efficiency of ion fragmentation, including the w-type fragment ion formation, and improves sequencing of peptides with multiple disulfide bridges. The developed instrumental configuration is essential for combined ECD and IRMPD on FTICR mass spectrometers with limited access into the ICR trap. PMID:12872281

  10. Toward understanding the dissociation of I2 in chemical oxygen-iodine lasers: Combined experimental and theoretical studies

    NASA Astrophysics Data System (ADS)

    Waichman, K.; Rybalkin, V.; Katz, A.; Dahan, Z.; Barmashenko, B. D.; Rosenwaks, S.

    2007-07-01

    The dissociation of I2 molecules at the optical axis of a supersonic chemical oxygen-iodine laser (COIL) was studied via detailed measurements and three-dimensional computational fluid dynamics calculations. The measurements, briefly reported in a recent paper [Rybalkin et al., Appl. Phys. Lett. 89, 021115 (2006)] and reanalyzed in detail here, revealed that the number N of consumed O2(aΔg1) molecules per dissociated I2 molecule depends on the experimental conditions: it is 4.5±0.4 for typical conditions and I2 densities applied for optimal operation of the COIL but increases at lower I2 densities. Comparing the measurements and the calculations enabled critical examination of previously proposed dissociation mechanisms and suggestion of a mechanism consistent with the experimental and theoretical results obtained in a supersonic COIL for the gain, temperature, I2 dissociation fraction, and N at the optical axis. The suggested mechanism combines the recent scheme of Azyazov and Heaven [AIAA J. 44, 1593 (2006)], where I2(A'Π2u3), I2(AΠ1u3), and O2(aΔg1,v) are significant dissociation intermediates, with the "standard" chain branching mechanism of Heidner III et al. [J. Phys. Chem. 87, 2348 (1983)], involving I(P1/22) and I2(XΣg +1,v).

  11. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    NASA Astrophysics Data System (ADS)

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-01

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O-/OH- and CH3- are recorded, indicating the low kinetic energies of O-/OH- for ethanol while the low and high kinetic energy distributions of O- ions for acetaldehyde. The CH3- image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O- ion via the dehydrogenated intermediate, CH3CHO- (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH3- is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  12. Characterization of water dissociation on α-Al2O3(11[combining macron]02): theory and experiment.

    PubMed

    Wirth, Jonas; Kirsch, Harald; Wlosczyk, Sebastian; Tong, Yujin; Saalfrank, Peter; Campen, R Kramer

    2016-06-01

    The interaction of water with α-alumina (i.e. α-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with α-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined α-Al2O3(11[combining macron]02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrödinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm(-1). Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable. PMID:27109875

  13. Modeling pure methane hydrate dissociation using a numerical simulator from a novel combination of X-ray computed tomography and macroscopic data

    SciTech Connect

    Gupta, A.; Moridis, G.J.; Kneafsey, T.J.; Sloan, Jr., E.D.

    2009-08-15

    The numerical simulator TOUGH+HYDRATE (T+H) was used to predict the transient pure methane hydrate (no sediment) dissociation data. X-ray computed tomography (CT) was used to visualize the methane hydrate formation and dissociation processes. A methane hydrate sample was formed from granular ice in a cylindrical vessel, and slow depressurization combined with thermal stimulation was applied to dissociate the hydrate sample. CT images showed that the water produced from the hydrate dissociation accumulated at the bottom of the vessel and increased the hydrate dissociation rate there. CT images were obtained during hydrate dissociation to confirm the radial dissociation of the hydrate sample. This radial dissociation process has implications for dissociation of hydrates in pipelines, suggesting lower dissociation times than for longitudinal dissociation. These observations were also confirmed by the numerical simulator predictions, which were in good agreement with the measured thermal data during hydrate dissociation. System pressure and sample temperature measured at the sample center followed the CH{sub 4} hydrate L{sub w}+H+V equilibrium line during hydrate dissociation. The predicted cumulative methane gas production was within 5% of the measured data. Thus, this study validated our simulation approach and assumptions, which include stationary pure methane hydrate-skeleton, equilibrium hydrate-dissociation and heat- and mass-transfer in predicting hydrate dissociation in the absence of sediments. It should be noted that the application of T+H for the pure methane hydrate system (no sediment) is outside the general applicability limits of T+H.

  14. Dissociative electron attachments to ethanol and acetaldehyde: A combined experimental and simulation study

    SciTech Connect

    Wang, Xu-Dong; Xuan, Chuan-Jin; Feng, Wen-Ling; Tian, Shan Xi

    2015-02-14

    Dissociation dynamics of the temporary negative ions of ethanol and acetaldehyde formed by the low-energy electron attachments is investigated by using the anion velocity map imaging technique and ab initio molecular dynamics simulations. The momentum images of the dominant fragments O{sup −}/OH{sup −} and CH{sub 3}{sup −} are recorded, indicating the low kinetic energies of O{sup −}/OH{sup −} for ethanol while the low and high kinetic energy distributions of O{sup −} ions for acetaldehyde. The CH{sub 3}{sup −} image for acetaldehyde also shows the low kinetic energy. With help of the dynamics simulations, the fragmentation processes are qualitatively clarified. A new cascade dissociation pathway to produce the slow O{sup −} ion via the dehydrogenated intermediate, CH{sub 3}CHO{sup −} (acetaldehyde anion), is proposed for the dissociative electron attachment to ethanol. After the electron attachment to acetaldehyde molecule, the slow CH{sub 3}{sup −} is produced quickly in the two-body dissociation with the internal energy redistributions in different aspects before bond cleavages.

  15. A combined electron-ion spectrometer for studying complete kinematics of molecular dissociation upon shell selective ionization

    SciTech Connect

    Saha, K.; Banerjee, S. B.; Bapat, B.

    2013-07-15

    A combined electron-ion spectrometer has been built to study dissociation kinematics of molecular ions upon various electronic decay processes ensuing from ionization of neutral molecules. The apparatus can be used with various ionization agents. Ion time-of-flight (ToF) spectra arising from various electronic decay processes are acquired by triggering the ToF measurement in coincidence with energy analyzed electrons. The design and the performance of the spectrometer in a photoionization experiment is presented in detail. Electron spectra and ion time of flight spectra resulting from valence and 2p{sub 1/2} ionization of Argon and those from valence ionization of CO are presented to demonstrate the capability of the instrument. The fragment ion spectra show remarkable differences (both kinematic and cross sectional) dependent on the energy of the ejected electron, corresponding to various electron loss and decay mechanisms in dissociative photoionization of molecules.

  16. Combined TMS and FMRI reveal dissociable cortical pathways for dynamic and static face perception.

    PubMed

    Pitcher, David; Duchaine, Bradley; Walsh, Vincent

    2014-09-01

    Faces contain structural information, for identifying individuals, as well as changeable information, which can convey emotion and direct attention. Neuroimaging studies reveal brain regions that exhibit preferential responses to invariant [1, 2] or changeable [3-5] facial aspects but the functional connections between these regions are unknown. We addressed this issue by causally disrupting two face-selective regions with thetaburst transcranial magnetic stimulation (TBS) and measuring the effects of this disruption in local and remote face-selective regions with functional magnetic resonance imaging (fMRI). Participants were scanned, over two sessions, while viewing dynamic or static faces and objects. During these sessions, TBS was delivered over the right occipital face area (rOFA) or right posterior superior temporal sulcus (rpSTS). Disruption of the rOFA reduced the neural response to both static and dynamic faces in the downstream face-selective region in the fusiform gyrus. In contrast, the response to dynamic and static faces was doubly dissociated in the rpSTS. Namely, disruption of the rOFA reduced the response to static but not dynamic faces, while disruption of the rpSTS itself reduced the response to dynamic but not static faces. These results suggest that dynamic and static facial aspects are processed via dissociable cortical pathways that begin in early visual cortex, a conclusion inconsistent with current models of face perception [6-9]. PMID:25131678

  17. Effect of Basic Residue on the Kinetics of Peptide Fragmentation Examined Using Surface-Induced Dissociation Combined with Resonant Ejection

    SciTech Connect

    Laskin, Julia

    2015-11-30

    In this work, resonant ejection coupled with surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer is used to examine fragmentation kinetics of two singly protonated hexapeptides, RYGGFL and KYGGFL, containing the basic arginine residue and less basic lysine residue at the N-terminus. The kinetics of individual reaction channels at different collision energies are probed by applying a short ejection pulse (1 ms) in resonance with the cyclotron frequency of a selected fragment ion and varying the delay time between ion-surface collision and resonant ejection while keeping total reaction delay time constant. Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental data provides accurate threshold energies and activation entropies of individual reaction channels. Substitution of arginine with less basic lysine has a pronounced effect on the observed fragmentation kinetics of several pathways, including the b2 ion formation, but has little or no effect on formation of the b5+H2O fragment ion. The combination of resonant ejection SID, time- and collision energy-resolved SID, and RRKM modeling of both types of experimental data provides a detailed mechanistic understanding of the primary dissociation pathways of complex gaseous ions.

  18. Combined CASSCF and MR-CI study on photoinduced dissociation and isomerization of acryloyl chloride.

    PubMed

    Cui, Gang-Long; Li, Qian-Song; Zhang, Feng; Fang, Wei-Hai; Yu, Jian-Guo

    2006-10-26

    The potential energy surfaces of isomerization and dissociation reactions for CH2CHCOCl in the S0, T1, T2, and S1 states have been mapped with DFT, CASSCF, MP2, and MR-CI calculations. Rate constants for adiabatic and nonadiabatic processes have been calculated with the RRKM rate theory, in conjugation with the vibronic interaction method. Mechanistic photochemistry of CH2CHCOCl at 230-310 nm has been characterized through the computed potential energy surfaces and rate constants. Upon photoexcitation of CH2CHCOCl at 310 nm, the S1-->T1 intersystem crossing is the dominant primary process, which is followed by the 1,3-Cl migration along the T1 pathway. Meanwhile, the S1-->S0 internal conversion occurs with considerable probability and the subsequent trans-cis isomerization proceeds in the ground state. The C-Cl bond cleavage is an exclusive primary channel upon photoexcitation of gaseous CH2CHCOCl at 230 nm. The direct C-Cl bond cleavage is partially blocked by effects of the matrix, and the internal conversion from S1 to S0 becomes an important process for the excited molecule to deactivate in the condensed phase. The present calculations not only provide a reasonable explanation of the experimental findings, but also give new insight into the mechanistic photochemistry of CH2CHCOCl. PMID:17048815

  19. Combined use of ion mobility and collision-induced dissociation to investigate the opening of disulfide bridges by electron-transfer dissociation in peptides bearing two disulfide bonds.

    PubMed

    Massonnet, Philippe; Upert, Gregory; Smargiasso, Nicolas; Gilles, Nicolas; Quinton, Loïc; De Pauw, Edwin

    2015-01-01

    Disulfide bonds are post-translational modifications (PTMs) often found in peptides and proteins. They increase their stability toward enzymatic degradations and provide the structure and (consequently) the activity of such folded proteins. The characterization of disulfide patterns, i.e., the cysteine connectivity, is crucial to achieve a global picture of the active conformation of the protein of interest. Electron-transfer dissociation (ETD) constitutes a valuable tool to cleave the disulfide bonds in the gas phase, avoiding chemical reduction/alkylation in solution. To characterize the cysteine pairing, the present work proposes (i) to reduce by ETD one of the two disulfide bridges of model peptides, resulting in the opening of the cyclic structures, (ii) to separate the generated species by ion mobility, and (iii) to characterize the species using collision-induced dissociation (CID). Results of this strategy applied to several peptides show different behaviors depending on the connectivity. The loss of SH· radical species, observed for all the peptides, confirms the cleavage of the disulfides during the ETD process. PMID:25915795

  20. New Approach for Studying Slow Fragmentation Kinetics in FT-ICR: Surface-Induced Dissociation Combined with Resonant Ejection

    SciTech Connect

    Laskin, Julia; Futrell, Jean H.

    2015-02-01

    We introduce a new approach for studying the kinetics of large ion fragmentation in the gas phase by coupling surface-induced dissociation (SID) in a Fourier transform ion cyclotron resonance mass spectrometer with resonant ejection of selected fragment ions using a relatively short (5 ms) ejection pulse. The approach is demonstrated for singly protonated angiotensin III ions excited by collisions with a self-assembled monolayer of alkylthiol on gold (HSAM). The overall decomposition rate and rate constants of individual reaction channels are controlled by varying the kinetic energy of the precursor ion in a range of 65–95 eV. The kinetics of peptide fragmentation are probed by varying the delay time between resonant ejection and fragment ion detection at a constant total reaction time. RRKM modeling indicates that the shape of the kinetics plots is strongly affected by the shape and position of the energy deposition function (EDF) describing the internal energy distribution of the ion following ion-surface collision. Modeling of the kinetics data provides detailed information on the shape of the EDF and energy and entropy effects of individual reaction channels.

  1. Spondylopelvic dissociation.

    PubMed

    Sullivan, Matthew P; Smith, Harvey E; Schuster, James M; Donegan, Derek; Mehta, Samir; Ahn, Jaimo

    2014-01-01

    Spondylopelvic dissociation is a complex injury pattern resulting in multiplanar instability of the lumbopelvis. These injuries have traditionally been known as "suicide jumper's fractures" and have recently increased in prevalence as a result of under-vehicle explosions seen in the past decade of military conflicts in the Middle East. The hallmarks of spondylopelvic dissociation are bilateral vertical sacral fractures with a horizontal component, resulting in lumbosacral instability in the sagittal and axial planes. Surgical treatment has evolved greatly and both percutaneous and open options are available, with triangular osteosynthesis being the most relied on method of fixation. PMID:24267208

  2. Compound ES of cytochrome c peroxidase contains a Trp {pi}-cation radical. Characterization by CW and pulsed Q-band ENDOR spectroscopy

    SciTech Connect

    Huyett, J.E.; Doan, P.E.; Gurbiel, R.; Houseman, A.L.P.; Sivaraja, M.; Hoffman, B.M.; Goodin, D.B.

    1995-09-06

    The fully oxidized state of cytochrome c peroxidase (CcP), called ES, contains two oxidizing equivalents, one as an oxyferryl heme and the other as an organic radical on an amino acid residue. The unusual electron paramagnetic resonance spectrum of ES has been shown to be due to a weak distributed exchange coupling between the two paramagnetic redox centers. Various residues have been proposed as the radical site over the years. In this paper continuous wave and pulsed Q-band electron nuclear double resonance (ENDOR) spectroscopy confirms that the radical is located on Trp-191, as previously proposed. The paper completes the characterization of the active site of compound ES as being comprized of an oxyferryl heme coupled to the Trp-191 {pi}-cation radical by a weak spin exchange. 47 refs., 11 figs., 2 tabs.

  3. Dissociative disorders in DSM-5.

    PubMed

    Spiegel, David; Lewis-Fernández, Roberto; Lanius, Ruth; Vermetten, Eric; Simeon, Daphne; Friedman, Matthew

    2013-01-01

    The rationale, research literature, and proposed changes to the dissociative disorders and conversion disorder in the fifth edition of the Diagnostic and Statistical Manual of Mental Disorders (DSM-5) are presented. Dissociative identity disorder will include reference to possession as well as identity fragmentation, to make the disorder more applicable to culturally diverse situations. Dissociative amnesia will include dissociative fugue as a subtype, since fugue is a rare disorder that always involves amnesia but does not always include confused wandering or loss of personality identity. Depersonalization disorder will include derealization as well, since the two often co-occur. A dissociative subtype of posttraumatic stress disorder (PTSD), defined by the presence of depersonalization or derealization in addition to other PTSD symptoms, is being recommended, based upon new epidemiological and neuroimaging evidence linking it to an early life history of adversity and a combination of frontal activation and limbic inhibition. Conversion disorder (functional neurological symptom disorder) will likely remain with the somatic symptom disorders, despite considerable dissociative comorbidity. PMID:23394228

  4. Dissociated Vertical Deviation

    MedlinePlus

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  5. Combined electron capture and infrared multiphoton dissociation for multistage MS/MS in a Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Håkansson, Kristina; Chalmers, Michael J; Quinn, John P; McFarland, Melinda A; Hendrickson, Christopher L; Marshall, Alan G

    2003-07-01

    We have mounted a permanent on-axis dispenser cathode electron source inside the magnet bore of a 9.4-T Fourier transform ion cyclotron resonance mass spectrometer. This configuration allows electron capture dissociation (ECD) to be performed reliably on a millisecond time scale. We have also implemented an off-axis laser geometry that enables simultaneous access to ECD and infrared multiphoton dissociation (IRMPD). Optimum performance of both fragmentation techniques is maintained. The analytical utility of performing either ECD or IRMPD on a given precursor ion population is demonstrated by structural characterization of several posttranslationally modified peptides: IRMPD of phosphorylated peptides results in few backbone (b- and y-type) cleavages, and product ion spectra are dominated by neutral loss of H3PO4. In contrast, ECD provides significantly more backbone (c- and z*-type) cleavages without loss of H3PO4. For N-glycosylated tryptic peptides, IRMPD causes extensive cleavage of the glycosidic bonds, providing structural information about the glycans. ECD cleaves all backbone bonds (except the N-terminal side of proline) in a 3-kDa glycopeptide with no saccharide loss. However, only a charge-reduced radical species and some side chain losses are observed following ECD of a 5-kDa glycopeptide from the same protein. An MS3 experiment involving IR laser irradiation of the charge-reduced species formed by electron capture results in extensive dissociation into c- and z-type fragment ions. Mass-selective external ion accumulation is essential for the structural characterization of these low-abundance (modified) peptides. PMID:12964777

  6. Tailored Noise Waveform/ Collision-Induced Dissociation of Ions Stored in a Linear Ion Trap Combined with Liquid Chromatography/Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

    SciTech Connect

    Vilkov, Andrey N.; Bogdanov, Bogdan; Pasa-Tolic, Liljiana; Prior, David C.; Anderson, Gordon A.; Masselon, Christophe D.; Moore, Ronald J.; Smith, Richard D.

    2004-11-01

    A new collision-induced dissociation (CID) technique based on broadband tailored noise waveform (TNW) excitation of ions stored in a linear ion trap has been developed. In comparison with the conventional sustained off-resonance irradiation (SORI) CID method commonly used in Fourier transform ion cyclotron resonance mass spectrometry, this MS/MS technique increases throughput by eliminating the long pump-down delay associated with gas introduction into the high vacuum ICR cell region. In addition, the TNW-CID method speeds spectrum acquisition since it does not require Fourier transformation, calculation of resonant frequencies and generation of the excitation waveforms. We demonstrate TNW-CID coupled with on-line capillary reverse phase liquid chromatography separations for identification of peptides. The experimental results are compared with data obtained using conventional quadrupole ion trap MS/MS and SORI-CID MS/MS in an ICR cell.

  7. Products of Dissociative Recombination in the Ionosphere

    NASA Technical Reports Server (NTRS)

    Cosby, Philip

    1996-01-01

    SRI International undertook a novel experimental measurement of the product states formed by dissociative ro-combination (DR) of C2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and ro-vibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates.

  8. Investigation of the Abstraction and Dissociation Mechanism in the Nitrogen Trifluoride Channels: Combined Post-Hartree-Fock and Transition State Theory Approaches.

    PubMed

    Claudino, D; Gargano, R; Carvalho-Silva, Valter H; E Silva, Geraldo M; da Cunha, W F

    2016-07-21

    The present paper concludes our series of kinetics studies on the reactions involved in the complex mechanism of nitrogen trifluoride decomposition. Two other related reactions that, along with this mechanism, take part in an efficient boron nitride growth process are also investigated. We report results concerning two abstraction reactions, namely NF2 + N ⇄ 2NF and NF3 + NF ⇄ 2NF2, and two dissociations, N2F4 ⇄ 2NF2 and N2F3 ⇄ NF2 + NF. State-of-the-art electronic structure calculations at the CCSD(T)/cc-pVTZ level of theory were considered to determine geometries and frequencies of reactants, products, and transition states. Extrapolation of the energies to the complete basis set limit was used to obtain energies of all the species. We applied transition state theory to compute thermal rate constants including Wigner, Eckart, Bell, and deformed theory corrections in order to take tunneling effects into account. The obtained results are in good agreement with the experimental data available in the literature and are expected to provide a better phenomenological understanding of the NF3 decomposition role in the boron nitride growth for a wide range of temperature values. PMID:27355487

  9. Imaging the molecular dynamics of dissociative electron attachment to water

    SciTech Connect

    Adaniya, Hidihito; Rudek, B.; Osipov, Timur; Haxton, Dan; Weber, Thorsten; Rescigno, Thomas N.; McCurdy, C.W.; Belkacem, Ali

    2009-10-19

    Momentum imaging experiments on dissociative electron attachment to the water molecule are combined with ab initio theoretical calculations of the angular dependence of the quantum mechanical amplitude for electron attachment to provide a detailed picture of the molecular dynamics of dissociation attachment via the two lowest energy Feshbach resonances. The combination of momentum imaging experiments and theory can reveal dissociation dynamics for which the axial recoil approximation breaks down and thus provides a powerful reaction microscope for DEA to polyatomics.

  10. A combined kick-out and dissociative diffusion mechanism of grown-in Be in InGaAs and InGaAsP. A new finite difference-Bairstow method for solution of the diffusion equations

    SciTech Connect

    Koumetz, Serge D. Martin, Patrick; Murray, Hugues

    2014-09-14

    Experimental results on the diffusion of grown-in beryllium (Be) in indium gallium arsenide (In{sub 0.53}Ga{sub 0.47}As) and indium gallium arsenide phosphide (In{sub 0.73}Ga{sub 0.27}As{sub 0.58}P{sub 0.42}) gas source molecular beam epitaxy alloys lattice-matched to indium phosphide (InP) can be successfully explained in terms of a combined kick-out and dissociative diffusion mechanism, involving neutral Be interstitials (Be{sub i}{sup 0}), singly positively charged gallium (Ga), indium (In) self-interstitials (I{sub III}{sup +}) and singly positively charged Ga, In vacancies (V{sub III}{sup +}). A new numerical method of solution to the system of diffusion equations, based on the finite difference approximations and Bairstow's method, is proposed.

  11. The dissociative bond.

    PubMed

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other. PMID:23282044

  12. Combined photoelectron, collision-induced dissociation, and computational studies of parent and fragment anions of N-paranitrophenylsulfonylalanine and N-paranitrophenylalanine

    SciTech Connect

    Lambert, Jason; Chen, Jing; Buonaugurio, Angela; Bowen, Kit H. E-mail: kbowen@jhu.edu; Do-Thanh, Chi-Linh; Wang, Yilin; Best, Michael D.; Compton, R. N. E-mail: kbowen@jhu.edu; Sommerfeld, Thomas

    2013-12-14

    After synthesizing the compounds N-paranitrophenylsulfonylalanine (NPNPSA) and N-paranitrophenylalanine (NPNPA), the photoelectron spectrum of the valence anion of N-paranitrophenylsulfonylalanine (NPNPSA){sup −}, was measured and the collision-induced dissociation (CID) pathways of deprotonated N-paranitrophenylsulfonylalanine (NPNPSA-H){sup −} and deprotonated N-paranitrophenylalanine (NPNPA-H){sup −} were determined. Pertinent calculations were conducted to analyze both sets of experimental data. From the valence anion photoelectron spectrum of (NPNPSA){sup −}, the adiabatic electron affinity (AEA) of NPNPSA was determined to be 1.7 ± 0.1 eV, while the vertical detachment energy (VDE) of (NPNPSA){sup −} was found to be 2.3 ± 0.1 eV. Calculations for four low lying conformers of (NPNPSA){sup −} gave AEA values in the range of 1.6–2.1 eV and VDE values in the range of 2.0–2.4 eV. These calculations are in very good agreement with the experimental values. While the NPNPA anion (NPNPSA){sup −} was not observed experimentally it was studied computationally. The six low lying (NPNPSA){sup −} conformers were identified and calculated to have AEA values in the range of 0.7–1.2 eV and VDE values in the range of 0.9–1.6 eV. CID was used to study the fragmentation patterns of deprotonated NPNPA and deprotonated NPNPSA. Based on the CID data and calculations, the excess charge was located on the delocalized π-orbitals of the nitrobenzene moiety. This is made evident by the fact that the dominant fragments all contained the nitrobenzene moiety even though the parent anions used for the CID study were formed via deprotonation of the carboxylic acid. The dipole-bound anions of both molecules are studied theoretically using the results of previous studies on nitrobenzene as a reference.

  13. Dissociation of diatomic gases

    NASA Technical Reports Server (NTRS)

    Hansen, C. F.

    1991-01-01

    The Landau-Zener theory of reactive cross sections has been applied to diatomic molecules dissociating from a ladder of rotational and vibrational states. Although the preexponential factor of the Arrhenius rate expression is shown to be a complex function of the dimensionless activation energy, the average over all states in the ladder is well represented by a single factor that varies about as T exp (-n), where the coefficient n is the order of unity. This relation agrees very well with experimental data for dissociation of O2 and N2, for example. The results validate previous empirical assignment of a single preexponential factor in the Arrhenius expression and justify the extrapolation of the expression well beyond the range of data. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators the results are about the same as for harmonic oscillators, and the dissociation from a ladder of equilibrium rotational and nonequilibrium vibrational states is close to an analytic approximation provided by Hammerling, Kivel, and Teare for harmonic oscillators all dissociating from the ground rotational state.

  14. An unusual family of glycosylated peptides isolated from Dendroaspis angusticeps venom and characterized by combination of collision induced and electron transfer dissociation.

    PubMed

    Quinton, Loïc; Gilles, Nicolas; Smargiasso, Nicolas; Kiehne, Andrea; De Pauw, Edwin

    2011-11-01

    This study describes the structural characterization of a totally new family of peptides from the venom of the snake green mamba (Dendroaspis angusticeps). Interestingly, these peptides differ in several points from other already known mamba toxins. First of all, they exhibit very small molecular masses, ranging from 1.3 to 2.4 kDa. The molecular mass of classical mamba toxins is in the range of 7 to 25 kDa. Second, the new peptides do not contain disulfide bonds, a post-translational modification commonly encountered in animal toxins. The third difference is the very high proportion of proline residues in the sequence accounting for about one-third of the sequence. Finally, these new peptides reveal a carbohydrate moiety, indicating a glycosylation in the sequence. The last two features have made the structural characterization of the new peptides by mass spectrometry a real analytical challenge. Peptides were characterized by a combined use of MALDI- TOF/TOF and nanoESI-IT-ETD experiments to determine not only the peptide sequence but also the composition and the position of the carbohydrate moiety. Anyway, such small glycosylated and proline-rich toxins are totally different from any other known snake peptide and form, as a consequence, a new family of peptides. PMID:21952754

  15. Predicting pressure-dependent unimolecular rate constants using variational transition state theory with multidimensional tunneling combined with system-specific quantum RRK theory: a definitive test for fluoroform dissociation.

    PubMed

    Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

    2016-06-22

    Understanding the falloff in rate constants of gas-phase unimolecular reaction rate constants as the pressure is lowered is a fundamental problem in chemical kinetics, with practical importance for combustion, atmospheric chemistry, and essentially all gas-phase reaction mechanisms. In the present work, we use our recently developed system-specific quantum RRK theory, calibrated by canonical variational transition state theory with small-curvature tunneling, combined with the Lindemann-Hinshelwood mechanism, to model the dissociation reaction of fluoroform (CHF3), which provides a definitive test for falloff modeling. Our predicted pressure-dependent thermal rate constants are in excellent agreement with experimental values over a wide range of pressures and temperatures. The present validation of our methodology, which is able to include variational transition state effects, multidimensional tunneling based on the directly calculated potential energy surface along the tunneling path, and torsional and other vibrational anharmonicity, together with state-of-the-art reaction-path-based direct dynamics calculations, is important because the method is less empirical than models routinely used for generating full mechanisms, while also being simpler in key respects than full master equation treatments and the full reduced falloff curve and modified strong collision methods of Troe. PMID:27273734

  16. Dissociative Reactions to Incest.

    ERIC Educational Resources Information Center

    Hall, J. Mark

    In contrast to Freud's later and revised view of the etiology of hysterical, or dissociative, symptoms, it is now known that real, and not fantasized, sexual experiences in childhood are experienced in disociative symptomatology. It is useful to understand that incest involves both traumatic events, that is, incidents of sexual violation per se,…

  17. Dissociative Identity Disorder

    ERIC Educational Resources Information Center

    Schmidt, Tom

    2007-01-01

    Few psychological disorders in the Diagnostic Statistical Manual have generated as much controversy as Dissociative Identity Disorder (DID). For the past 35 years diagnoses of DID, previously referred to as Multiple Personality Disorder (MPD), have increased exponentially, causing various psychological researchers and clinicians to question the…

  18. Pathological Dissociation as Measured by the Child Dissociative Checklist

    ERIC Educational Resources Information Center

    Wherry, Jeffrey N.; Neil, Debra A.; Taylor, Tamara N.

    2009-01-01

    The component structure of the Child Dissociative Checklist was examined among abused children. A factor described as pathological dissociation emerged that was predicted by participants being male. There also were differences in pathological dissociation between groups of sexually abused and physically abused children. Replication of this factor…

  19. Dissociation and psychosis in dissociative identity disorder and schizophrenia.

    PubMed

    Laddis, Andreas; Dell, Paul F

    2012-01-01

    Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia. PMID:22651674

  20. Traumatic dissociation as a predictor of posttraumatic stress disorder in South African female rape survivors.

    PubMed

    Nöthling, Jani; Lammers, Kees; Martin, Lindi; Seedat, Soraya

    2015-04-01

    Women survivors of rape are at an increased risk for posttraumatic stress disorder (PTSD). Traumatic dissociation has been identified as a precursor of PTSD. This study assessed the predictive potential of traumatic dissociation in PTSD and depression development.The study followed a longitudinal, prospective design. Ninety-seven female rape survivors were recruited from 2 clinics in Cape Town, South Africa. Clinical interviews and symptom status assessments of the participants were completed to measure dissociation, childhood traumas, resilience, depression, and PTSD.Traumatic dissociation was a significant predictor of PTSD and depression. The linear combination of prior dissociation, current dissociation, and resilience significantly explained 20.7% of the variance in PTSD. Dissociation mediated the relationship between resilience and PTSD.As traumatic dissociation significantly predicts PTSD, its early identification and management may reduce the risk of developing PTSD. Interventions focused on promoting resilience may also be successful in reducing the risk of dissociation following rape. PMID:25906104

  1. Traumatic Dissociation as a Predictor of Posttraumatic Stress Disorder in South African Female Rape Survivors

    PubMed Central

    Nöthling, Jani; Lammers, Kees; Martin, Lindi; Seedat, Soraya

    2015-01-01

    Abstract Women survivors of rape are at an increased risk for posttraumatic stress disorder (PTSD). Traumatic dissociation has been identified as a precursor of PTSD. This study assessed the predictive potential of traumatic dissociation in PTSD and depression development. The study followed a longitudinal, prospective design. Ninety-seven female rape survivors were recruited from 2 clinics in Cape Town, South Africa. Clinical interviews and symptom status assessments of the participants were completed to measure dissociation, childhood traumas, resilience, depression, and PTSD. Traumatic dissociation was a significant predictor of PTSD and depression. The linear combination of prior dissociation, current dissociation, and resilience significantly explained 20.7% of the variance in PTSD. Dissociation mediated the relationship between resilience and PTSD. As traumatic dissociation significantly predicts PTSD, its early identification and management may reduce the risk of developing PTSD. Interventions focused on promoting resilience may also be successful in reducing the risk of dissociation following rape. PMID:25906104

  2. Three dimensions of dissociative amnesia.

    PubMed

    Dell, Paul F

    2013-01-01

    Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders. PMID:23282045

  3. Modeling the electron-impact dissociation of methane

    NASA Astrophysics Data System (ADS)

    Ziółkowski, Marcin; Vikár, Anna; Mayes, Maricris Lodriguito; Bencsura, Ákos; Lendvay, György; Schatz, George C.

    2012-12-01

    The product yield of the electron-impact dissociation of methane has been studied with a combination of three theoretical methods: R-matrix theory to determine the electronically inelastic collisional excitation cross sections, high-level electronic structure methods to determine excited states energies and derivative couplings, and trajectory surface hopping (TSH) calculations to determine branching in the dissociation of the methane excited states to give CH3, CH2, and CH. The calculations involve the lowest 24 excited-state potential surfaces of methane, up to the ionization energy. According to the R-matrix calculations, electron impact preferentially produces triplet excited states, especially for electron kinetic energies close to the dissociation threshold. The potential surfaces of excited states are characterized by numerous avoided and real crossings such that the TSH calculations show rapid cascading down to the lowest excited singlet or triplet states, and then slower the dissociation of these lowest states. Product branching for electron-impact dissociation was therefore estimated by combining the electron-impact excitation cross sections with TSH product branching ratios that were obtained from the lowest singlet and triplet states, with the singlet dissociation giving a comparable formation of CH2 and CH3 while triplet dissociation gives CH3 exclusively. The overall branching in electron-impact dissociation is dominated by CH3 over CH2. A small branching yield for CH is also predicted.

  4. Dissociation and psychotic symptoms.

    PubMed

    Steingard, S; Frankel, F H

    1985-08-01

    The literature on hysterical or brief reactive psychosis reflects great diversity both in clinical description and theoretical formulation. The authors describe the case of a 17-year-old girl who presented with a diagnosis of bipolar affective disorder, rapid cycling type, but who, in fact, was experiencing dissociative episodes manifested as psychotic states. The patient's successful treatment with hypnosis is described, along with the clinical and theoretical implications of the case. PMID:4025593

  5. Controllable dissociations of PH3 molecules on Si(001)

    NASA Astrophysics Data System (ADS)

    Liu, Qin; Lei, Yanhua; Shao, Xiji; Ming, Fangfei; Xu, Hu; Wang, Kedong; Xiao, Xudong

    2016-04-01

    We demonstrate for the first time to our knowledge that controllable dissociation of PH3 adsorption products PH x (x = 2, 1) can be realized by STM (scanning tunneling microscope) manipulation techniques at room temperature. Five dissociative products and their geometric structures are identified via combining STM experiments and first-principle calculations and simulations. In total we realize nine kinds of controllable dissociations by applying a voltage pulse among the PH3-related structures on Si(001). The dissociation rates of the five most common reactions are measured by the I-t spectrum method as a function of voltage. The suddenly increased dissociation rate at 3.3 V indicates a transition from multivibrational excitation to single-step excitation induced by inelastic tunneling electrons. Our studies prove that selectively breaking the chemical bonds of a single molecule on semiconductor surface by STM manipulation technique is feasible.

  6. Controllable dissociations of PH3 molecules on Si(001).

    PubMed

    Liu, Qin; Lei, Yanhua; Shao, Xiji; Ming, Fangfei; Xu, Hu; Wang, Kedong; Xiao, Xudong

    2016-04-01

    We demonstrate for the first time to our knowledge that controllable dissociation of PH3 adsorption products PHx (x = 2, 1) can be realized by STM (scanning tunneling microscope) manipulation techniques at room temperature. Five dissociative products and their geometric structures are identified via combining STM experiments and first-principle calculations and simulations. In total we realize nine kinds of controllable dissociations by applying a voltage pulse among the PH3-related structures on Si(001). The dissociation rates of the five most common reactions are measured by the I-t spectrum method as a function of voltage. The suddenly increased dissociation rate at 3.3 V indicates a transition from multivibrational excitation to single-step excitation induced by inelastic tunneling electrons. Our studies prove that selectively breaking the chemical bonds of a single molecule on semiconductor surface by STM manipulation technique is feasible. PMID:26894452

  7. Recurrent dissociative fugue.

    PubMed

    Mamarde, Abhishek; Navkhare, Praveen; Singam, Amrita; Kanoje, Akash

    2013-10-01

    Dissociative fugue is a rarely reported diagnostic entity. It is one of the least understood and yet clinically one of the most fascinating disorders in mental health. Here, we describe a case of fugue in a 32-year-old man who was brought to mental hospital with complete loss of memory for events pertaining to identity of self. This case illustrates the nature of presentation in hospital setting like mental hospital and effort taken to reintegrate his identity and reunite with his family. PMID:24379504

  8. THE DISSOCIATIVE TURN IN PSYCHOANALYSIS.

    PubMed

    Itzkowitz, Sheldon

    2015-06-01

    In his response to the Roundtable Discussions on what is effective in psychoanalytic psychotherapy, the author focuses on the renewed interest in the concept of dissociation that began to emerge toward the end of the 20th century. A contemporary psychoanalytic position informed by the impact of developmental trauma has led to an understanding of and interest in the dissociative mind. The actuality of trauma during infancy and early childhood is recognized as a key factor leading to the emergence of dissociative processes, the potential dissociative structuring of the mind, and mind being characterized by multiple, discontinuous, centers of consciousness. The therapeutic goal in the psychoanalytic work with fragmented patients is to establish communication and understanding between the dissociated self-states. The author offers two brief clinical examples of working with dissociated self-states. PMID:26177756

  9. Dissociative Electron Attachment

    NASA Astrophysics Data System (ADS)

    Arreola, Esmeralda; Esmeralda Arreola Collaboration; Leigh Hargreaves Collaboration

    Since the pioneering work of Boudiaffa et al., it has been understood that electrons, even with energies near or below the ionization threshold, are capable of initiating strand-breaks in human DNA. This discovery raised important questions for cancer treatments, since sub-ionizing electrons are known to be the most copiously produced secondary product of radiation therapy. But even to date these factors are largely excluded from dosimetry calculations. This lack of inclusion is, at least in part, certainly due to the dearth of fundamental data describing low-energy electron interactions with nucleotide molecules that form the basis of DNA. Understanding of how such slow electrons are able to damage DNA remains incomplete, but the strongly peaked nature of Boudiaffa et al.'s data gives strong hints at resonantly driven collision processes. DNA damage is therefore most likely driven by ``dissociative electron attachment'' (DEA). DEA is a rather complicated process to model due to the coupling of electronic and nuclear degrees of freedom in the molecule. At the California State University Fullerton, we are currently commissioning a new spectrometer to study dissociation channels, reaction rates and orientation effects in DEA collisions between slow electrons and nucleotide molecules. At the meeting we will present design parameters and commissioning data for this new apparatus.

  10. Dynamics of dissociative electron attachment to ammonia

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Trevisan, C. S.; Orel, A. E.; Slaughter, D. S.; Adaniya, H.; Belkacem, A.; Weyland, Marvin; Dorn, Alexander; McCurdy, C. W.

    2016-05-01

    Ab initio theoretical studies and momentum-imaging experiments are combined to provide a consistent picture of the dynamics of dissociative electron attachment to ammonia through its 5.5- and 10.5-eV resonance channels. The present study clarifies the character and symmetry of the anion states involved and the dynamics that leads to the observed fragment-ion channels, their branching ratios, and angular distributions.

  11. Hyperglycemia associated dissociative fugue (organic dissociative disorder) in an elderly

    PubMed Central

    Ram, Dushad; Ashoka, H. G; Gowdappa, Basavnna

    2015-01-01

    Inadequate glycemic control in patients with diabetes is known to be associated with psychiatric disorders such as depression, anxiety disorder, and cognitive impairment. However, dissociative syndrome has not been reported so far. Here we are reporting a case of repeated dissociative fugue associated with hyperglycemia, in an elderly with type II diabetes. Possible neurobiological mechanism has been discussed. PMID:26286620

  12. Dissociative States and Neural Complexity

    ERIC Educational Resources Information Center

    Bob, Petr; Svetlak, Miroslav

    2011-01-01

    Recent findings indicate that neural mechanisms of consciousness are related to integration of distributed neural assemblies. This neural integration is particularly vulnerable to past stressful experiences that can lead to disintegration and dissociation of consciousness. These findings suggest that dissociation could be described as a level of…

  13. Orientation-dependent dissociative charge transfer

    SciTech Connect

    Wu, W.; Prior, M.H.; Braeuning, H.

    1998-01-01

    Recoil-ion momentum spectroscopy and molecular fragment imaging techniques are combined to study dissociative electron capture from He by HeH{sup +} at 0.20-a.u. collision velocity. Groups of final HeH states which dissociate to ground or excited H and He atoms are separated. For each group, the experiment provides two-dimensional H fragment distributions with respect to the collision plane and for fixed transverse momentum transfer. These patterns show that the capture probability is highest for HeH{sup +} ions with their axis oriented normal to the scattering plane for two of the three groups populated. {copyright} {ital 1998} {ital The American Physical Society}

  14. Dissociation of I II in chemical oxygen-iodine lasers: experiment, modeling, and pre-dissociation by electrical discharge

    NASA Astrophysics Data System (ADS)

    Katz, A.; Waichman, K.; Dahan, Z.; Rybalkin, V.; Barmashenko, B. D.; Rosenwaks, S.

    2007-06-01

    The dissociation of I II molecules at the optical axis of a supersonic chemical oxygen-iodine laser (COIL) was studied via detailed measurements and three dimensional computational fluid dynamics calculations. Comparing the measurements and the calculations enabled critical examination of previously proposed dissociation mechanisms and suggestion of a mechanism consistent with the experimental and theoretical results obtained in a supersonic COIL for the gain, temperature and I II dissociation fraction at the optical axis. The suggested mechanism combines the recent scheme of Azyazov and Heaven (AIAA J. 44, 1593 (2006)), where I II(A' 3Π 2u), I II(A 3Π 1u) and O II(a1Δ g, v) are significant dissociation intermediates, with the "standard" chain branching mechanism of Heidner et al. (J. Phys. Chem. 87, 2348 (1983)), involving I(2P 1/2) and I II(X1Σ + g, v). In addition, we examined a new method for enhancement of the gain and power in a COIL by applying DC corona/glow discharge in the transonic section of the secondary flow in the supersonic nozzle, dissociating I II prior to its mixing with O II(1Δ). The loss of O II(1Δ) consumed for dissociation was thus reduced and the consequent dissociation rate downstream of the discharge increased, resulting in up to 80% power enhancement. The implication of this method for COILs operating beyond the specific conditions reported here is assessed.

  15. Dissociative absorption: An empirically unique, clinically relevant, dissociative factor.

    PubMed

    Soffer-Dudek, Nirit; Lassri, Dana; Soffer-Dudek, Nir; Shahar, Golan

    2015-11-01

    Research of dissociative absorption has raised two questions: (a) Is absorption a unique dissociative factor within a three-factor structure, or a part of one general dissociative factor? Even when three factors are found, the specificity of the absorption factor is questionable. (b) Is absorption implicated in psychopathology? Although commonly viewed as "non-clinical" dissociation, absorption was recently hypothesized to be specifically associated with obsessive-compulsive symptoms. To address these questions, we conducted exploratory and confirmatory factor analyses on 679 undergraduates. Analyses supported the three-factor model, and a "purified" absorption scale was extracted from the original inclusive absorption factor. The purified scale predicted several psychopathology scales. As hypothesized, absorption was a stronger predictor of obsessive-compulsive symptoms than of general psychopathology. In addition, absorption was the only dissociative scale that longitudinally predicted obsessive-compulsive symptoms. We conclude that absorption is a unique and clinically relevant dissociative tendency that is particularly meaningful to obsessive-compulsive symptoms. PMID:26241024

  16. Recurrent Episodes of Dissociative Fugue

    PubMed Central

    Angothu, Hareesh; Pabbathi, Lokeswar Reddy

    2016-01-01

    Dissociative fugue is rare entity to encounter with possible differentials of epilepsy and malingering. It is one of the dissociative disorders rarely seen in clinical practice more often because of the short lasting nature of this condition. This might also be because of organized travel of the individuals during the episodes and return to their families after the recovery from episodes. This is a case description of a patient who has experienced total three episodes of dissociative fugue. The patient has presented during the third episode and two prior episodes were diagnosed as fugue episodes retrospectively based on the history. Planned travel in this case by the patient to a distant location was prevented because of early diagnosis and constant vigilance till the recovery. As in this case, it may be more likely that persons with Dissociative fugue may develop similar episodes if they encounter exceptional perceived stress. However, such conclusions may require follow-up studies. PMID:27114633

  17. Global functioning and disability in dissociative disorders.

    PubMed

    Mueller-Pfeiffer, Christoph; Rufibach, Kaspar; Perron, Noelle; Wyss, Daniela; Kuenzler, Cornelia; Prezewowsky, Cornelia; Pitman, Roger K; Rufer, Michael

    2012-12-30

    Dissociative disorders are frequent comorbid conditions of other mental disorders. Yet, there is controversy about their clinical relevance, and little systematic research has been done on how they influence global functioning. Outpatients and day care patients (N=160) of several psychiatric units in Switzerland were assessed with the Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders (DSM)-IV Axis I Disorders, Structured Clinical Interview for DSM-IV Dissociative Disorders, Global Assessment of Functioning Scale, and World Health Organization Disability Assessment Schedule-II. The association between subjects with a dissociative disorder (N=30) and functional impairment after accounting for non-dissociative axis I disorders was evaluated by linear regression models. We found a proportion of 18.8% dissociative disorders (dissociative amnesia=0%, dissociative fugue=0.6%, depersonalization disorder=4.4%, dissociative identity disorder=7.5%, dissociative disorder-not-otherwise-specified=6.3%) across treatment settings. Adjusted for other axis I disorders, subjects with a comorbid dissociative identity disorder or dissociative disorder-not-otherwise-specified had a median global assessment of functioning score that was 0.86 and 0.88 times, respectively, the score of subjects without a comorbid dissociative disorder. These findings support the hypothesis that complex dissociative disorders, i.e., dissociative identity disorder and dissociative disorder-not-otherwise-specified, contribute to functional impairment above and beyond the impact of co-existing non-dissociative axis I disorders, and that they qualify as "serious mental illness". PMID:22578820

  18. LBBB with History of Complete Atrioventricular Dissociation Underwent Bipolar Hemiarthroplasty

    PubMed Central

    Kumar, Indirani H

    2016-01-01

    A 70-year-old female patient, known case of hypertension and incomplete Left bundle branch block (LBBB), posted for bipolar hemiarthroplasty. A geriatric patient with LBBB and systemic hypertension is a fatal combination; it may precipitate into complete AV dissociation during anaesthesia and surgical stress. We are reporting this interesting case as our patient had developed complete Atrioventricular (AV) dissociation when scheduled earlier for surgery and got postponed. We had given combined spinal epidural anaesthesia and managed successfully without any complication. PMID:27504385

  19. Dissociative experiences and dissociative minds: Exploring a nomological network of dissociative functioning.

    PubMed

    Schimmenti, Adriano

    2016-01-01

    In this study, the psychometric properties of the Dissociative Experiences Scale-II (DES-II) were tested in a sample of Italian adults, and a nomological network of dissociative functioning based on current psychodynamic research was examined. A total of 794 participants (55% females) ranging in age from 18 to 64 completed the DES-II and other measures of theory of mind, alexithymia, attachment style, and empathy. The Italian translation of the DES-II showed high internal consistency, adequate item-to-scale homogeneity, and good split-half reliability. A single-factor solution including the 8 items of pathological dissociation (DES-T) adequately fit the data. Participants who reported higher levels of dissociative experiences showed significantly lower scores on theory of mind and empathy than other participants. They also showed significantly higher scores on alexithymia, preoccupied attachment, and fearful attachment. Results of the study support the view that people who suffer from severe dissociative experiences may also have difficulties mentalizing and regulating affects and that they may feel uncomfortable in close relationships because they have a negative view of the self. This can inform clinical work with dissociative individuals, who could benefit from therapies that consider their potential problems with mentalization, empathy, affect regulation, and attachment. PMID:26507547

  20. Dissociative symptomatology in cancer patients

    PubMed Central

    Civilotti, Cristina; Castelli, Lorys; Binaschi, Luca; Cussino, Martina; Tesio, Valentina; Di Fini, Giulia; Veglia, Fabio; Torta, Riccardo

    2015-01-01

    Introduction: The utilization of the post-traumatic stress disorder (PTSD) diagnostic spectrum is currently being debated to categorize psychological adjustment in cancer patients. The aims of this study were to: (1) evaluate the presence of cancer-related traumatic dissociative symptomatology in a sample of cancer patients; (2) examine the correlation of cancer-related dissociation and sociodemographic and medical variables, anxiety, depression, and post-traumatic stress symptomatology; (3) investigate the predictors of cancer-related dissociation. Methods: Ninety-two mixed cancer patients (mean age: 58.94, ds = 10.13) recruited from two hospitals in northern Italy were administered a questionnaire on sociodemographic and medical characteristics, the Karnofsky Scale to measure the level of patient activity and medical care requirements, the Hospital Anxiety and Depression Scale (HADS) to evaluate the presence of anxiety and depression, the Impact of Event Scale Revised (IES-R) to assess the severity of intrusion, avoidance, and hypervigilance, and the Peritraumatic Dissociative Experiences Questionnaire (PDEQ) to quantify the traumatic dissociative symptomatology. Results: 31.5% of participants report a PDEQ score above the cutoff. The results indicated that dissociative symptomatology was positively correlated with HADS scores (HADS-Anxiety: r = 0.476, p < 0.001; HADS-Depression: r = 0.364, p < 0.001) and with IES-R scores (IES-R-Intrusion: r = 0.698, p < 0.001; IES-R-Avoidance: r = 0.619, p < 0.001; IES-R- Hypervigilance: r = 0.681, p < 0.001). A stepwise regression analysis was performed in order to find the predictors of cancer-related traumatic dissociative symptomatology. The results converged on a three predictor model revealing that IES-R-Intrusion, IES-R-Avoidance, and IES-R-Hyperarousal accounted for 53.9% of the explained variance. Conclusion: These findings allow us to hypothesize a specific psychological reaction which may be ascribed to the traumatic

  1. Dissociative Electron Attachment to Carbon Dioxide via the 8.2 eV Feshbach resonance

    SciTech Connect

    Slaughter, Dan; Adaniya, Hidihito; Rescigno, Tom; Haxton, Dan; Orel, Ann; McCurdy, Bill; Belkacem, Ali

    2011-08-17

    Momentum imaging experiments on dissociative electron attachment (DEA) to CO{sub 2} are combined with the results of ab initio calculations to provide a detailed and consistent picture of the dissociation dynamics through the 8.2 eV resonance, which is the major channel for DEA in CO{sub 2}. The present study resolves several puzzling misconceptions about this system.

  2. Diffraction dissociation at the LHC

    SciTech Connect

    Jenkovszky, Laszlo; Orava, Risto; Salii, Andrii

    2013-04-15

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  3. Diffraction dissociation at the LHC

    NASA Astrophysics Data System (ADS)

    Jenkovszky, László; Orava, Risto; Salii, Andrii

    2013-04-01

    We report on recent calculations of low missing mass single (SD) and double (DD) diffractive dissociation at LHC energies. The calculations are based on a dual-Regge model, dominated by a single Pomeron exchange. The diffractively excited states lie on the nucleon trajectory N*, appended by the isolated Roper resonance. Detailed predictions for the squared momentum transfer and missing mass dependence of the differential and integrated single-and double diffraction dissociation in the kinematical range of present and future LHC measurements are given.

  4. Dissociation of pleasure in psychopathology.

    PubMed

    Brown, S L

    1981-01-01

    This paper analyzes the development of the concept of dissociation from 19th century psychological theory through 20th century neurophysiological thought. Recent research is discussed, indicating that normal individuals show an "association" between emitted pleasurable behavior and self-perception of pleasurable activity, whereas depressives and schizophrenics show a lack of association, or "dissociation," between these measures. concomitantly, depressives show an abnormal degree of association between the experience and expression of negative affect. Such a discrepancy in systems of affect is considered as both an important pathological element in mental disorder and also as a valuable new research tool for studying etiology, differential diagnosis, and therapeutic efficacy in psychobiological illness. PMID:7005394

  5. [Gender differences in dissociative disorders].

    PubMed

    Spitzer, C; Freyberger, H J

    2008-01-01

    The relationship between mental illness, on the one hand, and sex and gender, on the other hand, has received interest since the beginning of medicine in antique times. A prototypical example of a seemingly woman-specific disease is hysteria. The term itself, which is derived from the Greek word for womb, denotes a psychosexual dimension comprising the current attitude towards sexuality and the dominating gender relationship. In addition, the colourful history of hysteria indicates that illness is not exclusively determined by biological factors, but also significantly by socio-cultural influences, for example in the treatment of hysterical women. Even nowadays, there is a wide-spread belief that dissociative symptoms and disorders, which have succeeded hysteria in current classification systems, are predominantly seen in women. However, empirical studies in the general population and in different clinical samples using sound instruments have indicated that dissociative symptoms do not differ between the genders. The seemingly dominance of dissociative disorders in women may also depend on the socio-cultural context, because men with dissociative disorders usually do not enter the general health system, but rather the legal system, i.e. they can be found in jail or forensic institutions. PMID:18185968

  6. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    NASA Astrophysics Data System (ADS)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  7. The return of dissociation as absence within absence.

    PubMed

    Gurevich, Hayuta

    2014-12-01

    My aim is to translate Ferenczi's central concepts of the intrapsychic impact and imprint of early developmental trauma into both revived and contemporary conceptualizations. The concept of dissociation was renounced by Freud, yet it is returning as a cornerstone of recent trauma theories. Ferenczi used the concept of "repression," but used it in the sense of an intrapsychic imprint of early external trauma that fragments consciousness, that is, as dissociation. Furthermore, early trauma is double: an absence of protection that threatens existence of the self, combined with an absence of attachment and of recognition of this threat and terror; thus it is an absence-within-absence. This contemporary conceptualization entails a widening of the intrapsychic realm to include an intersubjective one, and regards dissociation as a unique and complex intrapsychic absence, which is a negative of the external absence-within-absence in the early environment. PMID:25434884

  8. Does the tautomeric status of the adenine bases change upon the dissociation of the A*·A(syn) Topal-Fresco DNA mismatch? A combined QM and QTAIM atomistic insight.

    PubMed

    Brovarets', Ol'ha O; Zhurakivsky, Roman O; Hovorun, Dmytro M

    2014-02-28

    We have scrupulously explored the tautomerisation mechanism via the double proton transfer of the A*·A(syn) Topal-Fresco base mispair (C(s) symmetry), formed by the imino and amino tautomers of the adenine DNA base in the anti- and syn-conformations, respectively, bridging quantum-mechanical calculations with Bader's quantum theory of atoms in molecules. It was found that the A*·A(syn) ↔ A·A*(syn) tautomerisation is the asynchronous concerted process. It was established that the A*·A(syn) DNA mismatch is stabilized by the N6H···N6 (6.35) and N1H···N7 (6.17) hydrogen (H) bonds, whereas the A·A*(syn) base mispair (Cs) by the N6H···N6 (8.82) and N7H···N1 (9.78) H-bonds and the C8H···HC2 HH-bond (0.30 kcal mol(-1)). Using the sweeps of the energies of the intermolecular H-bonds, it was observed that the N6H···N6 and N1H···N7/N7H···N1 H-bonds are anti-cooperative and mutually weaken each other in the A*·A(syn) and A·A*(syn) mispairs. It was revealed that the A·A*(syn) DNA mismatch is a dynamically unstable structure with a short lifetime of 1.12 × 10(-13) s and any of its 6 low-frequency intermolecular vibrations can develop during this period of time. This observation makes it impossible to change the tautomeric status of the A bases upon the dissociation of the A*·A(syn) base mispair into the monomers during DNA replication. PMID:24418908

  9. Mechanical Dissociation of Retinal Neurons with Vibration

    NASA Astrophysics Data System (ADS)

    Motomura, Tamami; Hayashida, Yuki; Murayama, Nobuki

    The neuromorphic device, which implements the functions of biological neural circuits by means of VLSI technology, has been collecting much attention in the engineering fields in the last decade. Concurrently, progress in neuroscience research has revealed the nonlinear computation in single neuron levels, suggesting that individual neurons are not merely the circuit elements but computational units. Thus, elucidating the properties of neuronal signal processing is thought to be an essential step for developing the next generation of neuromorphic devices. In the present study, we developed a method for dissociating single neurons from specific sublayers of mammalian retinas with using no proteolytic enzymes but rather combining tissue incubation in a low-Ca2+ medium and the vibro-dissociation technique developed for the slices of brains and spinal cords previously. Our method took shorter time of the procedure, and required less elaborated skill, than the conventional enzymatic method did; nevertheless it yielded enough number of the cells available for acute electrophysiological experiments. The isolated retinal neurons were useful for measuring the nonlinear membrane conductances as well as the spike firing properties under the perforated-patch whole-cell configuration. These neurons also enabled us to examine the effects of proteolytic enzymes on the membrane excitability in those cells.

  10. Study of the dissociation of molecular hydrogen

    NASA Technical Reports Server (NTRS)

    Vessot, R. F. C.

    1981-01-01

    Dissociators used to obtain an RF plasma discharge for hydrogen masers and the test system used for operation and evaluation of the dissociators are described. A compact sorption cartridge using a graphite matrix is tested as part of a hydrogen scavenging system. Testing of a vacuum enclosed hydrogen dissociator suitable for long term operation in space is described.

  11. Two-temperature models for nitrogen dissociation

    NASA Astrophysics Data System (ADS)

    da Silva, M. Lino; Guerra, V.; Loureiro, J.

    2007-12-01

    Accurate sets of nitrogen state-resolved dissociation rates have been reduced to two-temperature (translational T and vibrational Tv) dissociation rates. The analysis of such two-temperature dissociation rates shows evidence of two different dissociation behaviors. For Tv < 0.3 T dissociation proceeds predominantly from the lower-lying vibrational levels, whereas for Tv > 0.3 T dissociation proceeds predominantly form the near-dissociative vibrational levels, with an abrupt change of behavior at Tv = 0.3 T. These two-temperature sets have then been utilized as a benchmark for the comparison against popular multitemperature dissociation models (Park, Hansen, Marrone-Treanor, Hammerling, Losev-Shatalov, Gordiets, Kuznetsov, and Macheret-Fridman). This has allowed verifying the accuracy of each theoretical model, and additionally proposing adequate values for any semi-empirical parameters present in the different theories. The Macheret-Fridman model, who acknowledges the existence of the two aforementioned dissociation regimes, has been found to provide significantly more accurate results than the other models. Although these different theoretical approaches have been tested and validated solely for nitrogen dissociation processes, it is reasonable to expect that the general conclusions of this work, regarding the adequacy of the different dissociation models, could be extended to the description of arbitrary diatomic dissociation processes.

  12. Photoleucine Survives Backbone Cleavage by Electron Transfer Dissociation. A Near-UV Photodissociation and Infrared Multiphoton Dissociation Action Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Shaffer, Christopher J.; Martens, Jonathan; Marek, Aleš; Oomens, Jos; Tureček, František

    2016-04-01

    We report a combined experimental and computational study aimed at elucidating the structure of N-terminal fragment ions of the c type produced by electron transfer dissociation of photo-leucine (L*) peptide ions GL*GGKX. The c 4 ion from GL*GGK is found to retain an intact diazirine ring that undergoes selective photodissociation at 355 nm, followed by backbone cleavage. Infrared multiphoton dissociation action spectra point to the absence in the c 4 ion of a diazoalkane group that could be produced by thermal isomerization of vibrationally hot ions. The c 4 ion from ETD of GL*GGK is assigned an amide structure by a close match of the IRMPD action spectrum and calculated IR absorption. The energetics and kinetics of c 4 ion dissociations are discussed.

  13. Photoleucine Survives Backbone Cleavage by Electron Transfer Dissociation. A Near-UV Photodissociation and Infrared Multiphoton Dissociation Action Spectroscopy Study.

    PubMed

    Shaffer, Christopher J; Martens, Jonathan; Marek, Aleš; Oomens, Jos; Tureček, František

    2016-07-01

    We report a combined experimental and computational study aimed at elucidating the structure of N-terminal fragment ions of the c type produced by electron transfer dissociation of photo-leucine (L*) peptide ions GL*GGKX. The c 4 ion from GL*GGK is found to retain an intact diazirine ring that undergoes selective photodissociation at 355 nm, followed by backbone cleavage. Infrared multiphoton dissociation action spectra point to the absence in the c 4 ion of a diazoalkane group that could be produced by thermal isomerization of vibrationally hot ions. The c 4 ion from ETD of GL*GGK is assigned an amide structure by a close match of the IRMPD action spectrum and calculated IR absorption. The energetics and kinetics of c 4 ion dissociations are discussed. Graphical Abstract ᅟ. PMID:27059977

  14. Photoleucine Survives Backbone Cleavage by Electron Transfer Dissociation. A Near-UV Photodissociation and Infrared Multiphoton Dissociation Action Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Shaffer, Christopher J.; Martens, Jonathan; Marek, Aleš; Oomens, Jos; Tureček, František

    2016-07-01

    We report a combined experimental and computational study aimed at elucidating the structure of N-terminal fragment ions of the c type produced by electron transfer dissociation of photo-leucine (L*) peptide ions GL*GGKX. The c 4 ion from GL*GGK is found to retain an intact diazirine ring that undergoes selective photodissociation at 355 nm, followed by backbone cleavage. Infrared multiphoton dissociation action spectra point to the absence in the c 4 ion of a diazoalkane group that could be produced by thermal isomerization of vibrationally hot ions. The c 4 ion from ETD of GL*GGK is assigned an amide structure by a close match of the IRMPD action spectrum and calculated IR absorption. The energetics and kinetics of c 4 ion dissociations are discussed.

  15. Coupling capillary zone electrophoresis with electron transfer dissociation and activated ion electron transfer dissociation for top-down proteomics.

    PubMed

    Zhao, Yimeng; Riley, Nicholas M; Sun, Liangliang; Hebert, Alexander S; Yan, Xiaojing; Westphall, Michael S; Rush, Matthew J P; Zhu, Guijie; Champion, Matthew M; Mba Medie, Felix; Champion, Patricia A DiGiuseppe; Coon, Joshua J; Dovichi, Norman J

    2015-01-01

    Top-down proteomics offers the potential for full protein characterization, but many challenges remain for this approach, including efficient protein separations and effective fragmentation of intact proteins. Capillary zone electrophoresis (CZE) has shown great potential for separation of intact proteins, especially for differentially modified proteoforms of the same gene product. To date, however, CZE has been used only with collision-based fragmentation methods. Here we report the first implementation of electron transfer dissociation (ETD) with online CZE separations for top-down proteomics, analyzing a mixture of four standard proteins and a complex protein mixture from the Mycobacterium marinum bacterial secretome. Using a multipurpose dissociation cell on an Orbitrap Elite system, we demonstrate that CZE is fully compatible with ETD as well as higher energy collisional dissociation (HCD), and that the two complementary fragmentation methods can be used in tandem on the electrophoretic time scale for improved protein characterization. Furthermore, we show that activated ion electron transfer dissociation (AI-ETD), a recently introduced method for enhanced ETD fragmentation, provides useful performance with CZE separations to greatly increase protein characterization. When combined with HCD, AI-ETD improved the protein sequence coverage by more than 200% for proteins from both standard and complex mixtures, highlighting the benefits electron-driven dissociation methods can add to CZE separations. PMID:25893372

  16. [Dis-social personality disorder].

    PubMed

    Habermeyer, E; Herpertz, S C

    2006-05-01

    Deviant behavior is gaining in clinical importance if it is founded on stable, characteristic, and enduring patterns of psychopathologically relevant personality traits which have their onset in childhood or adolescence. The classification of these traits shows variations, so that a distinction between the ICD-10 diagnosis of dis-social personality disorder, DSM-IV diagnosis of antisocial personality disorder, and the concept "psychopathy" is necessary. Our knowledge about the biological basis of antisocial behavior includes neurophysiologic, psychophysiologic, and genetic findings. Also relevant are results of neurotransmitter studies and structural resp. functional neuroimaging findings. Psychosocial risk factors include parental deficits, rejection, disregard, unstable relations, and abuse. Efficient psychotherapeutic treatment is cognitive-behavioral. Pharmacologic treatment is largely "off-label". The diagnosis of antisocial and dis-social personality disorders allows no conclusions on criminal responsibility. In addition to psychiatric diagnostics, considerations on the severity of the disorder and its effects on the ability to inhibit actions are necessary. PMID:16609871

  17. Coulomb dissociation of N,2120

    NASA Astrophysics Data System (ADS)

    Röder, Marko; Adachi, Tatsuya; Aksyutina, Yulia; Alcantara, Juan; Altstadt, Sebastian; Alvarez-Pol, Hector; Ashwood, Nicholas; Atar, Leyla; Aumann, Thomas; Avdeichikov, Vladimir; Barr, M.; Beceiro, Saul; Bemmerer, Daniel; Benlliure, Jose; Bertulani, Carlos; Boretzky, Konstanze; Borge, Maria J. G.; Burgunder, G.; Caamaño, Manuel; Caesar, Christoph; Casarejos, Enrique; Catford, Wilton; Cederkäll, Joakim; Chakraborty, S.; Chartier, Marielle; Chulkov, Leonid; Cortina-Gil, Dolores; Crespo, Raquel; Datta Pramanik, Ushasi; Diaz-Fernandez, Paloma; Dillmann, Iris; Elekes, Zoltan; Enders, Joachim; Ershova, Olga; Estrade, A.; Farinon, F.; Fraile, Luis M.; Freer, Martin; Freudenberger, M.; Fynbo, Hans; Galaviz, Daniel; Geissel, Hans; Gernhäuser, Roman; Göbel, Kathrin; Golubev, Pavel; Gonzalez Diaz, D.; Hagdahl, Julius; Heftrich, Tanja; Heil, Michael; Heine, Marcel; Heinz, Andreas; Henriques, Ana; Holl, Matthias; Ickert, G.; Ignatov, Alexander; Jakobsson, Bo; Johansson, Hâkan; Jonson, Björn; Kalantar-Nayestanaki, Nasser; Kanungo, Rituparna; Kelic-Heil, Aleksandra; Knöbel, Ronja; Kröll, Thorsten; Krücken, Reiner; Kurcewicz, J.; Kurz, Nikolaus; Labiche, Marc; Langer, Christoph; Le Bleis, Tudi; Lemmon, Roy; Lepyoshkina, Olga; Lindberg, Simon; Machado, Jorge; Marganiec, Justyna; Mostazo Caro, Magdalena; Movsesyan, Alina; Najafi, Mohammad Ali; Nilsson, Thomas; Nociforo, Chiara; Panin, Valerii; Paschalis, Stefanos; Perea, Angel; Petri, Marina; Pietri, S.; Plag, Ralf; Prochazka, A.; Rahaman, Md. Anisur; Rastrepina, Ganna; Reifarth, Rene; Ribeiro, Guillermo; Ricciardi, M. Valentina; Rigollet, Catherine; Riisager, Karsten; Rossi, Dominic; Sanchez del Rio Saez, Jose; Savran, Deniz; Scheit, Heiko; Simon, Haik; Sorlin, Olivier; Stoica, V.; Streicher, Branislav; Taylor, Jon; Tengblad, Olof; Terashima, Satoru; Thies, Ronja; Togano, Yasuhiro; Uberseder, Ethan; Van de Walle, J.; Velho, Paulo; Volkov, Vasily; Wagner, Andreas; Wamers, Felix; Weick, Helmut; Weigand, Mario; Wheldon, Carl; Wilson, G.; Wimmer, Christine; Winfield, J. S.; Woods, Philip; Yakorev, Dmitry; Zhukov, Mikhail; Zilges, Andreas; Zuber, Kai; R3B Collaboration

    2016-06-01

    Neutron-rich light nuclei and their reactions play an important role in the creation of chemical elements. Here, data from a Coulomb dissociation experiment on N,2120 are reported. Relativistic N,2120 ions impinged on a lead target and the Coulomb dissociation cross section was determined in a kinematically complete experiment. Using the detailed balance theorem, the 19N (n ,γ )20N and 20N (n ,γ ) 21N excitation functions and thermonuclear reaction rates have been determined. The 19 (n ,γ )20N rate is up to a factor of 5 higher at T <1 GK with respect to previous theoretical calculations, leading to a 10% decrease in the predicted fluorine abundance.

  18. [Prison psychosis and dissociative disorders].

    PubMed

    al Chaabani, S; Bataille, M

    2002-12-01

    Through a few clinical case histories stemming from their daily activities at the psychiatric section of the Lantin Prison, the authors propose to revisit the classic concept of Prison psychosis. They broaden its limits to include other psychotic and dissociative phenomena common to the jail population. This requires a strict differential diagnosis, allowing to eliminate some similar pathologies; nevertheless, some difficulties and imperfections persist. The development of the psychosis, the input from the jail architecture and milieu, the predisposing as well as facilitating factors linked to the personality of the inmate, and triggering phenomena are discussed. Finally, the comorbidity between these psychotic/dissociative phenomena and the borderline & histrionic personality disorders is envisaged. PMID:12632838

  19. [Clinical Handling of Patients with Dissociative Disorders].

    PubMed

    Okano, Kenichiro

    2015-01-01

    This paper discusses the way informed psychiatrists are expected to handle dissociative patients in clinical situations, with a specific focus on dissociative identity disorders and dissociative fugue. On the initial interview with dissociative patients, information on their history of trauma and any nascent dissociative symptoms in their childhood should be carefully obtained. Their level of stress in their current life should also be assessed in order to understand their symptomatology, as well as to predict their future clinical course. A psychoeducational approach is crucial; it might be helpful to give information on dissociative disorder to these patients as well as their family members in order to promote their adherence to treatment. Regarding the symptomatology of dissociative disorders, detailed symptoms and the general clinical course are presented. It was stressed that dissociative identity disorder and dissociative fugue, the most high-profile dissociative disorders, are essentially different in their etiology and clinical presentation. Dissociative disorders are often confused with and misdiagnosed as psychotic disorders, such as schizophrenia. Other conditions considered in terms of the differential diagnosis include borderline personality disorder as well as temporal lobe epilepsy. Lastly, the therapeutic approach to dissociative identity disorder is discussed. Each dissociative identity should be understood as potentially representing some traumatically stressful event in the past. The therapist should be careful not to excessively promote the creation or elaboration of any dissociative identities. Three stages are proposed in the individual psychotherapeutic process. In the initial stage, a secure environment and stabilization of symptoms should be sought. The second stage consists of aiding the "host" personality to make use of other more adaptive coping skills in their life. The third stage involves coaching as well as continuous awareness of

  20. The Child Behavior Checklist as an indicator of posttraumatic stress disorder and dissociation in normative, psychiatric, and sexually abused children.

    PubMed

    Sim, Leslie; Friedrich, William N; Davies, W Hobart; Trentham, Bart; Lengua, Liliana; Pithers, William

    2005-12-01

    Expert ratings and confirmatory factor analyses were used to derive a posttraumatic stress disorder (PTSD), dissociation, and a combined PTSD/dissociation scale from the Child Behavior Checklist (CBCL). Validity was established by examining the relationship of these scales to features of sexual abuse thought to relate to severity and chronicity, as well as to self-report scales of PTSD and dissociation. In addition, this study examined differences between normative, psychiatric, and sexually abused children on the new scales. Both the sexual abuse and psychiatric sample differed significantly from the normative sample on all scales, but not from each other. Despite correlations of the dissociation and PTSD/dissociation combined scale with features of trauma and child self-report of PTSD and dissociation, the absence of differences between the clinical groups on the derived scales suggests that the scales measure generic, as opposed to trauma-related, distress. PMID:16382422

  1. Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

    NASA Astrophysics Data System (ADS)

    Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

    2014-03-01

    Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

  2. Religious Dissociation and Economic Appraisal in Brazil.

    PubMed

    François Dengah, H J

    2016-04-01

    Research on the association between religion and health often neglects to provide an explicit theoretical mechanism of influence between faith and well-being. This research posits that dissociative behaviors, such as glossolalia, may provide a biological pathway that influences both physiological and psychological health. This paper argues that religious dissociation acts as a moderator between economic stressors and psychobiological appraisal. Brazil, with its economic inequality and preponderance of religious dissociative rituals, provides an ideal context to examine religious dissociation as a moderator of stress. Utilizing data from a cross section of Brazilian faiths, this paper examines: (1) Whether individuals with low socioeconomic status preferentially participate and experience religious dissociative states and (2) whether dissociative states are correlated with greater psychological appraisal of status. PMID:25687180

  3. Dissociative Tendencies and Facilitated Emotional Processing

    PubMed Central

    Oathes, Desmond J.; Ray, William J.

    2009-01-01

    Dissociation is a process linked to lapses of attention, history of abuse or trauma, compromised emotional memory, and a disintegrated sense of self. It is theorized that dissociation stems from avoiding emotional information, especially negative emotion, to protect a fragile psyche. The present study tested whether or not dissociaters do actually avoid processing emotion by asking groups scoring high or low on the Dissociative Experiences Scale to judge the affective valence of several types of emotional stimuli. Manipulations of valence, modality (pictures or words), task complexity, and personal relevance lead to results suggesting that dissociation is linked to facilitated rather than deficient emotional processing. Our results are consistent with a theory that sensitivity to emotional material may be a contributing factor in subsequent dissociation to avoid further elaboration of upsetting emotion in these individuals. The findings for dissociation further exemplify the influence of individual differences in the link between cognition and emotion. PMID:18837615

  4. Coulomb Dissociation of 27P

    NASA Astrophysics Data System (ADS)

    Beceiro Novo, S.; Sümmerer, K.; Cortina-Gil, D.; Wimmer, C.; Plag, R.; Alvarez-Pol, H.; Aumann, T.; Behr, K.; Boretzky, K.; Casarejos, E.; Chatillon, A.; Datta-Pramanik, U.; Elekes, Z.; Fulop, Z.; Galaviz, D.; Geissel, H.; Giron, S.; Greife, U.; Hammache, F.; Heil, M.; Hoffman, J.; Johansson, H.; Karagiannis, C.; Kiselev, O.; Kurz, N.; Larsson, K.; Le Bleis, T.; Litvinov, Y.; Mahata, K.; Muentz, C.; Nociforo, C.; Ott, W.; Paschalis, S.; Prokopowicz, W.; Rodriguez-Tajes, C.; Rossi, D.; Simon, H.; Stanoiu, M.; Stroth, J.; Typel, S.; Wagner, A.; Wamers, F.; Weick, H.

    2012-09-01

    In this work the astrophysical 26Si(p,γ)27P reaction is studied using the Coulomb dissociation technique. We performed a 27P Coulomb Dissociation experiment at GSI, Darmstadt (28 May-5 June 2007) using the ALADIN-LAND setup which allows complete-kinematic studies. A secondary 27P beam at 498 AMeV impinging a 515mg/cm2 Pb target was used. The relative energy of the outgoing system (26Si+p) is measured obtaining the resonant states of the 27P. Preliminary results show four resonant states measured at 0.36±0.07, 0.88±0.09, 1.5±0.2, 2.3±0.3 MeV and evidence of a higher state at around 3.1 MeV. The preliminary total cross section obtained for relative energies between 0 and 3 MeV has been measured and yields 55±7 mb.

  5. Dissociative recombination in planetary ionospheres

    NASA Technical Reports Server (NTRS)

    Fox, J. L.

    1993-01-01

    Ionization in planetary atmospheres can be produced by solar photoionization, photoelectron impact ionization, and, in auroral regions, by impact of precipitating particles. This ionization is lost mainly in dissociative recombination (DR) of molecular ions. Although atomic ions cannot undergo DR, they can be transformed locally through ion-molecule reactions into molecular ions, or they may be transported vertically or horizontally to regions of the atmosphere where such transformations are possible. Because DR reactions tend to be very exothermic, they can be an important source of kinetically or internally excited fragments. In interplanetary thermospheres, the neutral densities decrease exponentially with altitude. Below the homopause (or turbopause), the atmosphere is assumed to be throughly mixed by convection and/or turbulence. Above the homopause, diffusion is the major transport mechanism, and each species is distributed according to its mass, with the logarithmic derivative of the density with repect to altitude given approximately by -1/H, where H = kT/mg is the scale height. In this expression, T is the neutral temperature, g is the local acceleratiion of gravity, and m is the mass of the species. Thus lighter species become relatively more abundant, and heavier species less abundant, as the altitude increases. This variation of the neutral composition can lead to changes in the ion composition; furthermore, as the neutral densities decrease, dissociative recombination becomes more important relative to ion-neutral reactions as a loss mechanism for molecular ions.

  6. Dissociative Recombination without a Curve Crossing

    NASA Technical Reports Server (NTRS)

    Guberman, Steven L.

    1994-01-01

    Ab initio calculations show that a curve crossing is not always needed for a high dissociative- recombination cross section. For HeH(+), in which no neutral states cross the ion potential curve, dissociative recombination is driven by the nuclear kinetic-energy operator on adiabatic potential curves. The kinetic-energy derivative operator allows for capture into repulsive curves that are outside of the classical turning points for the nuclear motion. The dominant dissociative route is the C (2)Sigma(+) state leading to H(n = 2) atoms. An analogous mechanism is proposed for the dissociative recombination of H3(+).

  7. Degree of somatoform and psychological dissociation in dissociative disorder is correlated with reported trauma.

    PubMed

    Nijenhuis, E R; Spinhoven, P; van Dyck, R; van der Hart, O; Vanderlinden, J

    1998-10-01

    In this study, the prevalence and severity of traumatic experiences as reported by patients with dissociative disorders and with other DSM-IV psychiatric diagnoses were compared. Furthermore, the predictive value of emotional, physical, and sexual trauma with respect to somatoform and psychological dissociation was analyzed. In contrast with comparison patients, dissociative disorder patients reported severe and multifaceted traumatization. Physical and sexual trauma predicted somatoform dissociation, sexual trauma predicted psychological dissociation as well. According to the memories of the dissociative disorder patients, this abuse occurred in an emotionally neglectful and abusive social context. Pathological dissociation was best predicted by early onset of reported intense, chronic and multiple traumatization. Methodological limitations restricting causal inferences between reported trauma and dissociation are discussed. PMID:9870223

  8. Dissociative symptoms and dissociative disorder comorbidity in patients with obsessive-compulsive disorder.

    PubMed

    Belli, Hasan; Ural, Cenk; Vardar, Melek Kanarya; Yesılyurt, Sema; Oncu, Fatıh

    2012-10-01

    The present study attempted to assess the dissociative symptoms and overall dissociative disorder comorbidity in patients with obsessive-compulsive disorder (OCD). In addition, we examined the relationship between the severity of obsessive-compulsive symptoms and dissociative symptoms. All patients admitted for the first time to the psychiatric outpatient unit were included in the study. Seventy-eight patients had been diagnosed as having OCD during the 2-year study period. Patients had to meet the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition criteria for OCD. Most (76.9%; n = 60) of the patients were female, and 23.1% (n = 18) of the patients were male. Dissociation Questionnaire was used to measure dissociative symptoms. The Structured Clinical Interview for Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition Dissociative Disorders interviews and Yale-Brown Obsessive Compulsive Checklist and Severity Scale were used. Eleven (14%) of the patients with OCD had comorbid dissociative disorder. The most prevalent disorder in our study was dissociative depersonalization disorder. Dissociative amnesia and dissociative identity disorder were common as well. The mean Yale-Brown score was 23.37 ± 7.27 points. Dissociation Questionnaire scores were between 0.40 and 3.87 points, and the mean was 2.23 ± 0.76 points. There was a statistically significant positive correlation between Yale-Brown points and Dissociation Questionnaire points. We conclude that dissociative symptoms among patients with OCD should alert clinicians for the presence of a chronic and complex dissociative disorder. Clinicians may overlook an underlying dissociative process in patients who have severe symptoms of OCD. However, a lack of adequate response to cognitive-behavioral and drug therapy may be a consequence of dissociative process. PMID:22425531

  9. Molecular dissociation in dilute gas

    SciTech Connect

    Renfrow, S.N.; Duggan, J.L.; McDaniel, F.D. |

    1999-06-01

    The charge state distributions (CSD) produced during molecular dissociation are important to both Trace Element Accelerator Mass Spectrometry (TEAMS) and the ion implantation industry. The CSD of 1.3{endash}1.7 MeV SiN{sup +}, SiMg{sup +}, SiMn{sup +}, and SiZn{sup +} molecules have been measured for elements that do not form atomic negative ions (N, Mg, Mn, and Zn) using a NEC Tandem Pelletron accelerator. The molecules were produced in a Cs sputter negative ion source, accelerated, magnetically analyzed, and then passed through an N{sub 2} gas cell. The neutral and charged breakups where analyzed using an electrostatic deflector and measured with particle detectors. Equilibrium CSD were determined and comparisons made between molecular and atomic ion data. {copyright} {ital 1999 American Institute of Physics.}

  10. The Dissociative Recombination of OH(+)

    NASA Technical Reports Server (NTRS)

    Guberman, Steven L.

    1995-01-01

    Theoretical quantum chemical calculations of the cross sections and rates for the dissociative recombination of the upsilon = 0 level of the ground state of OH(+) show that recombination occurs primarily along the 2 (2)Pi diabatic route. The products are 0((1)D) and a hot H atom with 6.1 eV kinetic energy. The coupling to the resonances is very small and the indirect recombination mechanism plays only a minor role. The recommended value for the rate coefficient is (6.3 +/- 0.7) x 10(exp -9)x (T(e)/1300)(exp -0.48) cu.cm/s for 10 less than T(e) less than 1000 K.

  11. Dissociative ionization of sodium molecules via repulsive Rydberg states

    NASA Astrophysics Data System (ADS)

    Chen, Hong

    In this thesis, an investigation of two color resonance multiphoton ionization (REMPI) and fragmentation processes in Na2 has been performed in combination with Linear Time-of-Flight Mass Spectrometry technique. The ionization and dissociative ionizations channels in the energy range up to 2500cm -1 above the dissociative ionization threshold into Na(3s)+Na ++e have been studied. After a mild supersonic expansion from the beam source, neutral sodium dimers in the ground state have been produced. Two tunable, pulsed lasers excite Na2 molecules via the intermediate A1S+u state to a single ro-vibrational level of the second intermediate 21pig state. Following absorption of a third photon, the total energy is above the dissociation limit into Na(3s) + Na+ + e. Typically, a small portion of atomic ions is produced under our experimental conditions. By varying the total available energy below and through the doubly excited states correlating with the Na(3p)+Na(4s) atom pair, there is no evidence that the doubly excited states positioned in the ionic continuum get involved. By calculation of the expected transition probabilities for all possible channels which can decay directly and indirectly into atomic ions, I find that direct dissociative ionization via 12S+u is impossible. The transition probabilities for dissociative ionization via the repulsive Rydberg states with principal quantum numbers n from 5˜12 converging toward the 12S+u state are three to four orders of magnitude larger than those for direct ionization into the continuum of the X2S+g ground state. These repulsive Rydberg states are much more likely to play a role in the photo-ionization through the intermediate 21Pg state. A semi-classical model which was originally developed for negative ion dissociative attachment (O'MAL'67) describes how dissociative ionization occurs along the repulsive Rydberg states. Its prediction concerning the ratio of atomic to molecular ion production as a function of initial

  12. Dissociative recombination of highly symmetric polyatomic ions.

    PubMed

    Douguet, Nicolas; Orel, Ann E; Greene, Chris H; Kokoouline, Viatcheslav

    2012-01-13

    A general first-principles theory of dissociative recombination is developed for highly symmetric molecular ions and applied to H(3)O(+) and CH(3)(+), which play an important role in astrophysical, combustion, and laboratory plasma environments. The theoretical cross sections obtained for the dissociative recombination of the two ions are in good agreement with existing experimental data from storage ring experiments. PMID:22324682

  13. A Hierarchical Process-Dissociation Model

    ERIC Educational Resources Information Center

    Rouder, Jeffrey N.; Lu, Jun; Morey, Richard D.; Sun, Dongchu; Speckman, Paul L.

    2008-01-01

    In fitting the process-dissociation model (L. L. Jacoby, 1991) to observed data, researchers aggregate outcomes across participant, items, or both. T. Curran and D. L. Hintzman (1995) demonstrated how biases from aggregation may lead to artifactual support for the model. The authors develop a hierarchical process-dissociation model that does not…

  14. Dissociation and the Development of Psychopathology.

    ERIC Educational Resources Information Center

    Putnam, Frank W.; Trickett, Penelope K.

    This paper reviews the research on dissociation and the development of psychopathology in children and adolescents. Definitions and dimensions of dissociation are addressed, noting its range from normative daydreaming to the extremes found in individuals with multiple personality disorder. Memory dysfunctions, disturbances of identity, passive…

  15. Dissociative depression among women in the community.

    PubMed

    Sar, Vedat; Akyüz, Gamze; Oztürk, Erdinç; Alioğlu, Firdevs

    2013-01-01

    This study screened the prevalence and correlates of dissociative disorders among depressive women in the general population. The Dissociative Disorders Interview Schedule and the posttraumatic stress disorder (PTSD) and borderline personality disorder sections of the Structured Clinical Interview for DSM-IV were administered to 628 women in 500 homes. The prevalence of current major depressive episode was 10.0%. Of the women, 26 (40.6%) had the lifetime diagnosis of a DSM-IV, dissociative disorder, yielding a prevalence of 4.1% for dissociative depression. This group was younger (mean age = 30.7 years) than the nondissociative depression women (mean age = 39.6 years). There was no difference between the 2 groups on comorbid somatization disorder, PTSD, or borderline personality disorder. Besides suicide attempts, the dissociative group was characterized by secondary features of dissociative identity disorder; Schneiderian symptoms; borderline personality disorder criteria; and extrasensory perceptions, including possession experiences. They reported suicidality, thoughts of guilt and worthlessness, diminished concentration and indecisiveness, and appetite and weight changes more frequently than the nondissociative group. Early cessation of school education and childhood sexual abuse were frequently reported by the dissociative depression group. With its distinct features, the concept of dissociative depression may facilitate understanding of treatment resistance in, development of better psychotherapy strategies for, and new thinking on the neurobiology and pharmacotherapy of depressive disorders. PMID:23796173

  16. Recent developments in the theory of dissociation

    PubMed Central

    SPITZER, CARSTEN; BARNOW, SVEN; FREYBERGER, HARALD J; GRABE, HANS JOERGEN

    2006-01-01

    Although the construct of dissociation was introduced into psychiatry at the end of the 19th century by Pierre Janet, the term still lacks a coherent conceptualization, which is partially reflected by differences in the classification of dissociative and conversion disorders in ICD-10 and DSM-IV. Given the clinical significance of dissociative psychopathology in numerous clinical conditions, it is very valuable that various efforts have been made to refine and to specify current conceptualizations in recent years. The most promising and convincing approaches converge in subdividing dissociation into qualitatively different types, i.e. pathological versus non-pathological dissociation, and "detachment" versus "compartmentalization". We review these concepts and discuss their scientific and clinical potential as well as their limitations. PMID:16946940

  17. The Shutdown Dissociation Scale (Shut-D)

    PubMed Central

    Schalinski, Inga; Schauer, Maggie; Elbert, Thomas

    2015-01-01

    The evolutionary model of the defense cascade by Schauer and Elbert (2010) provides a theoretical frame for a short interview to assess problems underlying and leading to the dissociative subtype of posttraumatic stress disorder. Based on known characteristics of the defense stages “fright,” “flag,” and “faint,” we designed a structured interview to assess the vulnerability for the respective types of dissociation. Most of the scales that assess dissociative phenomena are designed as self-report questionnaires. Their items are usually selected based on more heuristic considerations rather than a theoretical model and thus include anything from minor dissociative experiences to major pathological dissociation. The shutdown dissociation scale (Shut-D) was applied in several studies in patients with a history of multiple traumatic events and different disorders that have been shown previously to be prone to symptoms of dissociation. The goal of the present investigation was to obtain psychometric characteristics of the Shut-D (including factor structure, internal consistency, retest reliability, predictive, convergent and criterion-related concurrent validity). A total population of 225 patients and 68 healthy controls were accessed. Shut-D appears to have sufficient internal reliability, excellent retest reliability, high convergent validity, and satisfactory predictive validity, while the summed score of the scale reliably separates patients with exposure to trauma (in different diagnostic groups) from healthy controls. The Shut-D is a brief structured interview for assessing the vulnerability to dissociate as a consequence of exposure to traumatic stressors. The scale demonstrates high-quality psychometric properties and may be useful for researchers and clinicians in assessing shutdown dissociation as well as in predicting the risk of dissociative responding. PMID:25976478

  18. Dissociation and Memory Fragmentation in Posttraumatic Stress Disorder: An Evaluation of the Dissociative Encoding Hypothesis

    PubMed Central

    Bedard-Gilligan, Michele; Zoellner, Lori A.

    2012-01-01

    Several prominent theories of posttraumatic stress disorder (PTSD) posit that peritraumatic dissociation results in insufficient encoding of the trauma memory and that persistent dissociation prevents memory elaboration, resulting in memory fragmentation and PTSD. In this review, we summarize the empirical literature on peritraumatic and trait dissociation and trauma narrative fragmentation as measured by meta-memory and rater/objective coding. Across 16 studies to date, the association between dissociation and fragmentation was most prominent when examining peritraumatic dissociation and patient's own ratings of memory fragmentation. This relationship did not hold when examining trait dissociation or rater-coded or computer-generated measures of fragmentation. Thus, initial evidence points more toward a strong self-reported association between constructs that is not supported on more objective fragmentation coding. Measurement overlap, construct ambiguity, and exclusion of potential confounds may underlie lack of a strong association between dissociation and objective-rated fragmentation. PMID:22348400

  19. Shielding of CO from dissociating radiation in interstellar clouds

    NASA Technical Reports Server (NTRS)

    Glassgold, A. E.; Huggins, P. J.; Langer, W. D.

    1985-01-01

    The paper investigates the photodissociation of CO in interstellar clouds in the light of recent laboratory studies which suggest that line rather than continuum processes dominate its dissociation by ultraviolet radiation. Using a simple radiative transfer model, the shielding of representative dissociating bands is estimated, including self-shielding, mutual shielding between different isotopes, and near coincidences with strong lines of H2. Each of these processes materially affects the photodestruction rates of the various isotopic species in the transition regions of molecular clouds. These results are combined with an appropriate gas phase chemical model to determine how the abundances of the CO isotopes vary with depth into the cloud. It is found that self-shielding and mutual shielding cause significant variations in isotopic ratios. In addition, fractionation enhances species containing C-13. The relationship between the column densities of CO and H2 is found to vary for the different isotopes and to be sensitive to local conditions.

  20. From state dissociation to status dissociatus.

    PubMed

    Antelmi, Elena; Ferri, Raffaele; Iranzo, Alex; Arnulf, Isabelle; Dauvilliers, Yves; Bhatia, Kailash P; Liguori, Rocco; Schenck, Carlos H; Plazzi, Giuseppe

    2016-08-01

    The states of being are conventionally defined by the simultaneous occurrence of behavioral, neurophysiological and autonomic descriptors. State dissociation disorders are due to the intrusion of features typical of a different state into an ongoing state. Disorders related to these conditions are classified according to the ongoing main state and comprise: 1) Dissociation from prevailing wakefulness as seen in hypnagogic or hypnopompic hallucinations, automatic behaviors, sleep drunkenness, cataplexy and sleep paralysis 2) Dissociation from rapid eye movement (REM) sleep as seen in REM sleep behavior disorder and lucid dreaming and 3) Dissociation from NREM sleep as seen in the disorders of arousal. The extreme expression of states dissociation is characterized by the asynchronous occurrence of the various components of the different states that prevents the recognition of any state of being. This condition has been named status dissociatus. According to the underlying disorders/diseases and to their severity, among status dissociatus we may recognize disorders in which such an extreme dissociation occurs only at night time or intermittently (i.e., autoimmune encephalopathies, narcolepsy type 1 and IgLON5 parasomnia), and others in which it occurs nearly continuously with complete loss of any conventionally defined state of being, and of the circadian pattern (agrypnia excitata). Here, we render a comprehensive review of all diseases/disorders associated with state dissociation and status dissociatus and propose a critical classification of this complex scenario. PMID:26431902

  1. Dissociative Recombination of Molecular Ions for Astrochemistry

    NASA Astrophysics Data System (ADS)

    Savin, Daniel W.; Novotný, O.; Becker, A.; Buhr, H.; Geppert, W.; Hamberg, M.; Krantz, C.; Kreckel, H.; Schwalm, D.; Spruck, K.; Stützel, J.; Wolf, A.; Yang, B.

    2013-06-01

    Dissociative recombination (DR) of molecular ions is a key chemical process in the cold interstellar medium (ISM). DR affects the composition, charge state, and energy balance of such environments. Astrochemical models of the ISM require reliable total DR cross sections as well as knowledge of the chemical composition and excitation states of the neutral DR products. Theory cannot reliably provide these data. We have systematically measured DR for many astrophysically relevant molecular ions utilizing the TSR storage ring at the Max-Planck-Institute for Nuclear Physics in Heidelberg, Germany. We used the merged ion-electron beam technique combined with an energy- and position-sensitive imaging detector and are able to study DR down to plasma temperatures of 10 K. The DR count rate is used to obtain absolute DR rate coefficient. Additionally we determine the masses of the DR products by measuring their kinetic energy. This allows us to assign particular DR fragmentation channels and to obtain their branching ratios. Moreover, the distribution of detected fragment distances provides information on the kinetic energy released in DR and thus also on the internal excitation of the DR products. All this information is particularly important for understanding DR of heteronuclear polyatomic ions. We will present DR results for several ions recently investigated at TSR. This work is supported in part by NASA and the NSF.

  2. State dissociation, human behavior, and consciousness.

    PubMed

    Mahowald, Mark W; Cramer Bornemann, Michel A; Schenck, Carlos H

    2011-01-01

    Sleep is clearly not only a whole-brain or global phenomenon, but can also be a local phenomenon. This accounts for the fact that the primary states of being (wakefulness, NREM sleep, and REM sleep) are not necessarily mutually exclusive, and components of these states may appear in various combinations, with fascinating clinical consequences. Examples include: sleep inertia, narcolepsy, sleep paralysis, lucid dreaming, REM sleep behavior disorder, sleepwalking, sleep terrors, out-of-body experiences, and reports of alien abduction. The incomplete declaration of state likewise has implications for consciousness - which also has fluid boundaries. Fluctuations in the degree of consciousness are likely explained by abnormalities of a "spatial and temporal binding rhythm" which normally results in a unified conscious experience. Dysfunctional binding may play a role in anesthetic states, autism, schizophrenia, and neurodegenerative disorders. Further study of the broad spectrum of dissociated states of sleep and wakefulness that are closely linked with states of consciousness and unconsciousness by basic neuroscientists, clinicians, and members of the legal profession will provide scientific, clinical and therapeutic insights, with forensic implications. PMID:21906025

  3. The association-dissociation behavior of the ApoE proteins: kinetic and equilibrium studies

    PubMed Central

    Garai, Kanchan; Frieden, Carl

    2010-01-01

    The apolipoprotein E family consists of three major protein isoforms: apolipoprotein E4 (ApoE4), ApoE3 and ApoE2. The isoforms, which contain 299 residues, differ only by single amino acid changes but of the three only ApoE4 is a risk factor for Alzheimer’s Disease. At μM concentrations lipid-free ApoE exists predominantly as tetramers. In more dilute solutions, lower molecular weight species predominate. Using Fluorescence Correlation Spectroscopy (FCS), intermolecular Fluorescence Resonance Energy Transfer (FRET) and sedimentation methods we find that the association-dissociation reaction of ApoE can be modeled with a monomer-dimer-tetramer process. Equilibrium constants have been determined from the sedimentation data while the individual rate constants for association and dissociation are determined by measuring the kinetics of dissociation of ApoE and are in agreement with the equilibrium constants. Dissociation kinetics as measured by intermolecular FRET show two phases reflecting the dissociation of tetramer to dimer and of dimer to monomer with dissociation from tetramer to dimer being more rapid than the dimer to monomer dissociation. The rate constants differ for the different ApoE isoforms showing that the association-dissociation process is isoforms specific. Strikingly, the association rate constants are almost two orders of magnitude slower than expected for a diffusion controlled process. Dissociation kinetics were also monitored by tryptophan fluorescence in presence of acrylamide and the data found to be consistent with the monomer-dimer-tetramer model. The approach combining multiple methods establishes the reaction scheme of ApoE self-association. PMID:20923231

  4. Theory of dissociative tunneling ionization

    NASA Astrophysics Data System (ADS)

    Svensmark, Jens; Tolstikhin, Oleg I.; Madsen, Lars Bojer

    2016-05-01

    We present a theoretical study of the dissociative tunneling ionization process. Analytic expressions for the nuclear kinetic energy distribution of the ionization rates are derived. A particularly simple expression for the spectrum is found by using the Born-Oppenheimer (BO) approximation in conjunction with the reflection principle. These spectra are compared to exact non-BO ab initio spectra obtained through model calculations with a quantum mechanical treatment of both the electronic and nuclear degrees of freedom. In the regime where the BO approximation is applicable, imaging of the BO nuclear wave function is demonstrated to be possible through reverse use of the reflection principle, when accounting appropriately for the electronic ionization rate. A qualitative difference between the exact and BO wave functions in the asymptotic region of large electronic distances is shown. Additionally, the behavior of the wave function across the turning line is seen to be reminiscent of light refraction. For weak fields, where the BO approximation does not apply, the weak-field asymptotic theory describes the spectrum accurately.

  5. Wavepacket theory of collisional dissociation in molecules

    SciTech Connect

    Kulander, K.

    1980-01-01

    An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H/sub 2/ system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process.

  6. Dissociative Ionization of Pyridine by Electron Impact

    NASA Technical Reports Server (NTRS)

    Dateo, Christopher; Huo, Winifred; Kwak, Dochan (Technical Monitor)

    2002-01-01

    In order to understand the damage of biomolecules by electrons, a process important in radiation damage, we undertake a study of the dissociative ionization (DI) of pyridine (C5H5N) from the low-lying ionization channels. The methodology used is the same as in the benzene study. While no experimental DI data are available, we compare the dissociation products from our calculations with the dissociative photoionization measurements of Tixier et al. using dipole (e, e(+) ion) coincidence spectroscopy. Comparisons with the DI of benzene is also made so as to understand the difference in DI between a heterocyclic and an aromatic molecule.

  7. Dissociation of Natural and Artificial Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Misyura, S. Y.

    2016-02-01

    Present work deals with natural and artificial methane hydrate dissociation. The heating of the powder produced due to the temperature difference between the external air and the powder. The dissociation rate was determined by gravimetric method. The range of the partial self-preservation for the natural hydrate is significantly longer than for the artificial one and moved to higher temperatures. The destruction of the natural sample is slower than the artificial one. The time-averaged dissociation rate for the artificial sample is equal to 1,25 %/s and for the natural hydrate corresponds to 0,59 %/s.

  8. A new concept Tandem thermal dissociator/electron impact ion source for RIB generation

    SciTech Connect

    Alton, G.D.; Williams, C.

    1995-12-31

    An innovative thermal dissociation/electron impact ionization positive ion source is presently under design at the Oak Ridge National Laboratory for potential use for generating RIBs at the Holifield Radioactive Ion Beam Facility (HRIBF). Because of the low probability of simultaneously dissociating and efficiently ionizing the individual atomic constituents with conventional, hot-cathode, electron-impact ion sources, the ion beams extracted from these sources often appear as a mixture of several molecular sideband beams. In this way, the intensity of the species of interest is diluted. We have conceived an Ion source that combines the excellent molecular dissociation properties of a thermal dissociator and the high efficiency characteristics of an electron impact ionization source. If the concept proves to be a viable option, the source will be used as a complement to the electron beam plasma ion sources already in use at the HRIBF. The design features and principles of operation of the source are described in this article.

  9. Absolute total and partial dissociative cross sections of pyrimidine at electron and proton intermediate impact velocities

    SciTech Connect

    Wolff, Wania Luna, Hugo; Sigaud, Lucas; Montenegro, Eduardo C.; Tavares, Andre C.

    2014-02-14

    Absolute total non-dissociative and partial dissociative cross sections of pyrimidine were measured for electron impact energies ranging from 70 to 400 eV and for proton impact energies from 125 up to 2500 keV. MOs ionization induced by coulomb interaction were studied by measuring both ionization and partial dissociative cross sections through time of flight mass spectrometry and by obtaining the branching ratios for fragment formation via a model calculation based on the Born approximation. The partial yields and the absolute cross sections measured as a function of the energy combined with the model calculation proved to be a useful tool to determine the vacancy population of the valence MOs from which several sets of fragment ions are produced. It was also a key point to distinguish the dissociation regimes induced by both particles. A comparison with previous experimental results is also presented.

  10. Collision-induced gas phase dissociation rates

    NASA Technical Reports Server (NTRS)

    Hansen, C. Frederick

    1990-01-01

    The Landau-Zener theory of reactive cross sections was applied to diatomic molecules dissociating from a ladder of vibrational states. The result predicts a dissociation rate that is quite well duplicated by an Arrhenius function having a preexponential temperature dependence of about T(sub -1/2), at least for inert collision partners. This relation fits experimental data reasonably well. The theory is then used to calculate the effect of vibrational nonequilibrium on dissociation rate. For Morse oscillators, the results are about the same as given by Hammerling, Kivel, and Teare in their analytic approximation for harmonic oscillators, though at very high temperature a correction for the partition function limit is included. The empirical correction for vibration nonequilibrium proposed by Park, which is a convenient algorithm for CFD calculations, is modified to prevent a drastic underestimation of dissociation rates that occurs with this method when vibrational temperature is much smaller than the kinetic temperature of the gas.

  11. Dissociative identity disorder presenting as dermatitis artefacta.

    PubMed

    Ozmen, Mine; Erdogan, Ayten; Aydemir, Ertugrul H; Oguz, Oya

    2006-06-01

    Dermatitis artefacta is a rare psychiatric condition characterized by rubbing of skin blisters and denial of self-infliction. Dissociation may be comorbid with self-injurious behavior. A background of emotional disturbances during formative years and in later life often results in feelings of isolation and insecurity, which can lead to dissociation as a primary defense mechanism used to overcome traumatic events. In this case report, we describe a female patient with dermatitis artefacta associated with dissociative identity disorder. The patient was a 14-year-old girl. Multiple large, deep ulcerations with unnatural shapes were seen on her left forearm. The ulcerations were thought to be self-inflicted. Psychiatric examination revealed that she had a different identity, and inflicted the lesions when this was assumed. This case leads us to suggest that patients with dermatitis artefacta might have comorbid dissociative experiences, which cannot be identified easily. PMID:16796649

  12. Research Reports: Hallucinogens and Dissociative Drugs

    MedlinePlus

    ... in bizarre or dangerous behavior. Hallucinogens such as LSD, psilocybin, peyote, DMT, and ayahuasca cause emotions to ... Take Hallucinogenic or Dissociative Drugs? How Do Hallucinogens (LSD, Psilocybin, Peyote, DMT, and Ayahuasca) Affect the Brain ...

  13. Quantitative structure-(chromatographic) retention relationship models for dissociating compounds.

    PubMed

    Kubik, Łukasz; Wiczling, Paweł

    2016-08-01

    The aim of this work was to develop mathematical models relating the hydrophobicity and dissociation constant of an analyte with its structure, which would be useful in predicting analyte retention times in reversed-phase liquid chromatography. For that purpose a large and diverse group of 115 drugs was used to build three QSRR models combining retention-related parameters (logkw-chromatographic measure of hydrophobicity, S-slope factor from Snyder-Soczewinski equation, and pKa) with structural descriptors calculated by means of molecular modeling for both dissociated and nondissociated forms of analytes. Lasso, Stepwise and PLS regressions were used to build statistical models. Moreover a simple QSRR equations based on lipophilicity and dissociation constant parameters calculated in the ACD/Labs software were proposed and compared with quantum chemistry-based QSRR equations. The obtained relationships were further used to predict chromatographic retention times. The predictive performances of the obtained models were assessed using 10-fold cross-validation and external validation. The QSRR equations developed were simple and were characterized by satisfactory predictive performance. Application of quantum chemistry-based and ACD-based descriptors leads to similar accuracy of retention times' prediction. PMID:26960942

  14. Isomerization and dissociation in competition: The two-component dissociation rates of methyl propionate ions

    SciTech Connect

    Mazyar, O.A.; Baer, T.

    1999-03-04

    Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy has been used to investigate the unimolecular chemistry of gas-phase methyl propionate ions. This ion undergoes isomerization to a lower energy enol structure, CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+}, via two different pathways involving two distonic isomers, {sup {sm_bullet}}CH{sub 2}CH{sub 2}C{sup +}(OH)OCH{sub 3} and CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}}. This isomerization reaction is in competition with the direct CH{sub 3}O{sup {sm_bullet}} loss reaction, which leads to two-component dissociation rates of the methyl propionate ions. Detailed modeling of this complex reaction permitted the extraction of the dissociative photoionization threshold for methyl propionate, which at 0 K is 10.83 {+-} 0.01 eV, as well as the isomerization barrier between the distonic CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}} and enol CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+} ions of 8.5 kcal/mol (relative to the methyl propionate ion). By combining this with the 0 K heats of formation of methyl propionate and the methoxy radical, the authors derive a 0 K heat of formation of the product propanoyl ion of 147 kcal/mol. Also measured was the adiabatic ionization energy of methyl propionate, 10.03 {+-} 0.05 eV.

  15. Dissociation energy of molecules in dense gases

    NASA Technical Reports Server (NTRS)

    Kunc, J. A.

    1992-01-01

    A general approach is presented for calculating the reduction of the dissociation energy of diatomic molecules immersed in a dense (n = less than 10 exp 22/cu cm) gas of molecules and atoms. The dissociation energy of a molecule in a dense gas differs from that of the molecule in vacuum because the intermolecular forces change the intramolecular dynamics of the molecule, and, consequently, the energy of the molecular bond.

  16. STABILITY OF A SPHERICAL ACCRETION SHOCK WITH NUCLEAR DISSOCIATION

    SciTech Connect

    Fernandez, Rodrigo; Thompson, Christopher

    2009-06-01

    We examine the stability of a standing shock wave within a spherical accretion flow onto a gravitating star, in the context of core-collapse supernova explosions. Our focus is on the effect of nuclear dissociation below the shock on the linear growth, and nonlinear saturation, of nonradial oscillations of the shocked fluid. We combine two-dimensional, time-dependent hydrodynamic simulations using FLASH2.5 with a solution to the linear eigenvalue problem, and demonstrate the consistency of the two approaches. Previous studies of this 'standing accretion shock instability' (SASI) have focused either on zero-energy accretion flows without nuclear dissociation, or made use of a detailed finite-temperature nuclear equation of state and included strong neutrino heating. Our main goal in this and subsequent papers is to introduce equations of state of increasing complexity, in order to isolate the various competing effects. In this work, we employ an ideal gas equation of state with a constant rate of nuclear dissociation below the shock, and do not include neutrino heating. We find that a negative Bernoulli parameter below the shock significantly lowers the real frequency, growth rate, and saturation amplitude of the SASI. A decrease in the adiabatic index has similar effects. The nonlinear development of the instability is characterized by an expansion of the shock driven by turbulent kinetic energy at nearly constant internal energy. Our results also provide further insight into the instability mechanism: the rate of growth of a particular mode is fastest when the radial advection time from the shock to the accretor overlaps with the period of a standing lateral sound wave. The fastest-growing mode can therefore be modified by nuclear dissociation.

  17. Dissociative Ionization of Benzene by Electron Impact

    NASA Technical Reports Server (NTRS)

    Huo, Winifred; Dateo, Christopher; Kwak, Dochan (Technical Monitor)

    2002-01-01

    We report a theoretical study of the dissociative ionization (DI) of benzene from the low-lying ionization channels. Our approach makes use of the fact that electron motion is much faster than nuclear motion and DI is treated as a two-step process. The first step is electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model. For the unimolecular dissociation step, we study the steepest descent reaction path to the minimum of the ion potential energy surface. The path is used to analyze the probability of unimolecular dissociation and to determine the product distributions. Our analysis of the dissociation products and the thresholds of the productions are compared with the result dissociative photoionization measurements of Feng et al. The partial oscillator strengths from Feng et al. are then used in the iBED cross section calculations.

  18. Collision induced dissociation of alpha hydroxy acids

    NASA Astrophysics Data System (ADS)

    Bandu, Mary L.; Grubbs, Thomas; Kater, Marcus; Desaire, Heather

    2006-03-01

    Alpha hydroxy acids typically dissociate in tandem mass spectrometric experiments to produce product ions representing a neutral loss of 46 Da (CH2O2) in negative ion mode. Although it is widely accepted that the carboxylate group is lost in the dissociation process, the origin of the remaining two hydrogens is unclear. The current study utilizes an alpha hydroxy acid chemical library and deuterium labeling experiments to identify the origin of the two hydrogens lost during dissociation. Secondly, this study investigates the lower m/z region of the CID spectrum, a region previously unexplored, to aid in characterizing the dissociation mechanism. Further experiments testing the energy requirements and time parameters of the dissociation also are consistent with criteria previously defined for ion-neutral complex formation. In addition to describing the mechanism for the loss of CH2O2, we have conducted experiments that demonstrate the important chemical features of molecules that can prevent alpha hydroxy acids from undergoing the loss of 46 Da. By understanding the chemical composition of the 46 Da loss, the dissociation mechanism responsible for the loss, and the factors that hinder this mechanistic pathway, chemical information about alpha hydroxy acids can be obtained from their CID data.

  19. Unimolecular dissociation of cyclopentadiene and indene

    SciTech Connect

    Yi, W.; Chattopadhyay, A.; Bersohn, R. )

    1991-05-01

    The dissociation of hydrogen atoms from the methylene group of cyclopentadiene (CP) and indene (ID) excited with a 193 nm photon has been studied by hydrogen atom laser induced fluorescence. The rate of dissociation of IND was 7.4{times}10{sup 6} s{sup {minus}1} but that of CP was too fast to measure. The ratio of H atoms to D atoms generated from 5-deuteriocyclopentadiene (5-dCP) was 3.91{plus minus}0.46. Rice--Ramsberger--Kassel--Marcus theory was used to calculate the rates of dissociation of CP and 5-dCP. The quantum yield for dissociating H atoms from CP was 0.85{plus minus}0.07. The ejected H atoms have a Maxwell velocity distribution with temperatures which are equal to the vibrational temperatures, 3690 and 2479 K for CP and IND, respectively. The most important result of the work is this confirmation of an earlier finding on a different set of molecules that the translational temperature of the fragments {ital after} the dissociation is equal to the vibrational temperature {ital before} the dissociation. This is explained by the assumption that the motion of the fast, light hydrogen atom is partly decoupled from that of the heavier, slower atoms.

  20. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates.

    PubMed

    Kwon, Tae-Hyuk; Kneafsey, Timothy J; Rees, Emily V L

    2011-06-30

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO(2)) and/or production of methane (CH(4)) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH(4) and CO(2) hydrate (CH(4)-CO(2) mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH(4)-CO(2) mixed hydrates. We prepared CH(4)-CO(2) mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH(4)-CO(2) mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH(4)-CO(2) compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO(2) concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO(2) than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO(2) in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO(2) concentration in the vapor phase enriched the hydrate in CO(2). The dissociation enthalpy of the CH(4)-CO(2) mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH(4)-CO(2) mixed hydrate lays between the limiting values of pure CH(4) hydrate and CO(2) hydrate, increasing with the CO(2) fraction in the hydrate phase. PMID:21604671

  1. "Trip-Sitting" in the Black Hole: A Netnographic Study of Dissociation and Indigenous Harm Reduction.

    PubMed

    Hearne, Evelyn; Van Hout, Marie Claire

    2016-01-01

    An array of dissociative novel psychoactive substances, including "methoxetamine," "3-MeO-PCP," and "methoxphenidine," have emerged as substitutes for the illicit substance "ketamine." A netographic research methodology aimed to describe online, dissociative novel psychoactive substance users' perceptions of risk, informed knowledge around use, and indigenous harm-reduction practices as advocated within online drug fora, so as to provide credible information which can be used to inform public online health education and drug prevention. Systematic Internet searches were performed using the terms "synthetic dissociative," "methoxetamine," "methoxphenidine," "diphenidine," "3-MeO-PCP," "4-MeO-PCP," "2-MDP," and "dissociative research chemical" in combination with "forum." Following screening of 3,476 forum threads with removal of duplicates and exclusion criteria, 90 user trip reports and 115 fora threads from seven drug fora websites were analyzed by conducting content analysis. Five themes emerged with 43 categories. The findings illustrated how forum activity within the cyber drug user community disseminated and exchanged "communal folk pharmacology" relating to the use of dissociative novel psychoactive substances. Further research and consistent monitoring of Internet drug fora are advised to explore variations in harm-reduction tactics throughout dissociative NPS populations, and to consider how existing harm-reduction initiatives are influencing these hard-to-reach groups. PMID:27430659

  2. Generating Breathable Air Through Dissociation of N2O

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Frankie, Brian

    2006-01-01

    includes one or more "destroyer" subsystems for removing any nitrogen oxides that remain downstream of the main N2O-dissociation reactor. A destroyer includes a carbon bed in series with a catalytic reactor, and is in thermal contact with the main N2O-dissociation reactor. The gas mixture that leaves the main reactor first goes through a carbon bed, which adsorbs all of the trace NO and most of the trace NO2. The gas mixture then goes through the destroyer catalytic reactor, wherein most or all of the remaining NO2 is dissociated. A NOBOSS can be designed to regulate its reactor temperature across a range of flow rates. One such system includes three destroyer loops; these loops act, in combination with a heat sink, to remove heat from the main N2O-dissociation reactor. In this system, the N2O and product gases play an additional role as coolants; thus, as needed, the coolant flow increases in proportion to the rate of generation of heat, helping to keep the main-reactor temperature below 540 C.

  3. Dissociations between developmental dyslexias and attention deficits

    PubMed Central

    Lukov, Limor; Friedmann, Naama; Shalev, Lilach; Khentov-Kraus, Lilach; Shalev, Nir; Lorber, Rakefet; Guggenheim, Revital

    2014-01-01

    We examine whether attention deficits underlie developmental dyslexia, or certain types of dyslexia, by presenting double dissociations between the two. We took into account the existence of distinct types of dyslexia and of attention deficits, and focused on dyslexias that may be thought to have an attentional basis: letter position dyslexia (LPD), in which letters migrate within words, attentional dyslexia (AD), in which letters migrate between words, neglect dyslexia, in which letters on one side of the word are omitted or substituted, and surface dyslexia, in which words are read via the sublexical route. We tested 110 children and adults with developmental dyslexia and/or attention deficits, using extensive batteries of reading and attention. For each participant, the existence of dyslexia and the dyslexia type were tested using reading tests that included stimuli sensitive to the various dyslexia types. Attention deficit and its type was established through attention tasks assessing sustained, selective, orienting, and executive attention functioning. Using this procedure, we identified 55 participants who showed a double dissociation between reading and attention: 28 had dyslexia with normal attention and 27 had attention deficits with normal reading. Importantly, each dyslexia with suspected attentional basis dissociated from attention: we found 21 individuals with LPD, 13 AD, 2 neglect dyslexia, and 12 surface dyslexia without attention deficits. Other dyslexia types (vowel dyslexia, phonological dyslexia, visual dyslexia) also dissociated from attention deficits. Examination of 55 additional individuals with both a specific dyslexia and a certain attention deficit found no attention function that was consistently linked with any dyslexia type. Specifically, LPD and AD dissociated from selective attention, neglect dyslexia dissociated from orienting, and surface dyslexia dissociated from sustained and executive attention. These results indicate that

  4. Dissociative Recombination of Molecular Ions for Astrochemistry

    NASA Astrophysics Data System (ADS)

    Novotny, Oldrich; Becker, A.; Buhr, H.; Fleischmann, Andreas; Gamer, Lisa; Geppert, W.; Krantz, C.; Kreckel, H.; Schwalm, D.; Spruck, K.; Wolf, A.; Savin, Daniel Wolf

    2014-06-01

    Dissociative recombination (DR) of molecular ions is a key chemical process in the cold interstellar medium (ISM). DR affects the composition, charge state, and energy balance of such environments. Astrochemical models of the ISM require reliable total DR cross sections as well as knowledge of the chemical composition of the neutral DR products. We have systematically measured DR for many astrophysically relevant molecular ions utilizing the TSR storage ring at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg, Germany. We used the merged ion-electron beam technique combined with an energy- and position-sensitive imaging detector and are able to study DR down to plasma temperatures as low as 10 K. The DR count rate is used to obtain an absolute merged beams DR rate coefficient from which we can derive a thermal rate coefficient needed for plasma models. Additionally we determine the masses of the DR products by measuring their kinetic energy in the laboratory reference frame. This allows us to assign particular DR fragmentation channels and to obtain their branching ratios. All this information is particularly important for understanding DR of heteronuclear polyatomic ions. We will present DR results for several ions recently investigated at TSR. A new Cryogenic Storage Ring (CSR) is currently being commissioned at MPIK. With the chamber cooled down to ~10 K and a base pressure better than 10-13 mbar, this setup will allow internal cooling of the stored ions down to their rotational ground states, thus opening a new era in DR experiments. New technological challenges arise due to the ultracold, ultra-high vacuum environment of the CSR and thus the detection techniques used at TSR cannot be easily transferred to CSR. We will present new approaches for DR fragment detection in cryogenic environment. This work is supported in part by NASA and the NSF.

  5. Electromagnetic Dissociation and Spacecraft Electronics Damage

    NASA Technical Reports Server (NTRS)

    Norbury, John W.

    2016-01-01

    When protons or heavy ions from galactic cosmic rays (GCR) or solar particle events (SPE) interact with target nuclei in spacecraft, there can be two different types of interactions. The more familiar strong nuclear interaction often dominates and is responsible for nuclear fragmentation in either the GCR or SPE projectile nucleus or the spacecraft target nucleus. (Of course, the proton does not break up, except possibly to produce pions or other hadrons.) The less familiar, second type of interaction is due to the very strong electromagnetic fields that exist when two charged nuclei pass very close to each other. This process is called electromagnetic dissociation (EMD) and primarily results in the emission of neutrons, protons and light ions (isotopes of hydrogen and helium). The cross section for particle production is approximately defined as the number of particles produced in nucleus-nucleus collisions or other types of reactions. (There are various kinematic and other factors which multiply the particle number to arrive at the cross section.) Strong, nuclear interactions usually dominate the nuclear reactions of most interest that occur between GCR and target nuclei. However, for heavy nuclei (near Fe and beyond) at high energy the EMD cross section can be much larger than the strong nuclear interaction cross section. This paper poses a question: Are there projectile or target nuclei combinations in the interaction of GCR or SPE where the EMD reaction cross section plays a dominant role? If the answer is affirmative, then EMD mechanisms should be an integral part of codes that are used to predict damage to spacecraft electronics. The question can become more fine-tuned and one can ask about total reaction cross sections as compared to double differential cross sections. These issues will be addressed in the present paper.

  6. Dissociable Learning Processes Underlie Human Pain Conditioning.

    PubMed

    Zhang, Suyi; Mano, Hiroaki; Ganesh, Gowrishankar; Robbins, Trevor; Seymour, Ben

    2016-01-11

    Pavlovian conditioning underlies many aspects of pain behavior, including fear and threat detection [1], escape and avoidance learning [2], and endogenous analgesia [3]. Although a central role for the amygdala is well established [4], both human and animal studies implicate other brain regions in learning, notably ventral striatum and cerebellum [5]. It remains unclear whether these regions make different contributions to a single aversive learning process or represent independent learning mechanisms that interact to generate the expression of pain-related behavior. We designed a human parallel aversive conditioning paradigm in which different Pavlovian visual cues probabilistically predicted thermal pain primarily to either the left or right arm and studied the acquisition of conditioned Pavlovian responses using combined physiological recordings and fMRI. Using computational modeling based on reinforcement learning theory, we found that conditioning involves two distinct types of learning process. First, a non-specific "preparatory" system learns aversive facial expressions and autonomic responses such as skin conductance. The associated learning signals-the learned associability and prediction error-were correlated with fMRI brain responses in amygdala-striatal regions, corresponding to the classic aversive (fear) learning circuit. Second, a specific lateralized system learns "consummatory" limb-withdrawal responses, detectable with electromyography of the arm to which pain is predicted. Its related learned associability was correlated with responses in ipsilateral cerebellar cortex, suggesting a novel computational role for the cerebellum in pain. In conclusion, our results show that the overall phenotype of conditioned pain behavior depends on two dissociable reinforcement learning circuits. PMID:26711494

  7. Dissociable Learning Processes Underlie Human Pain Conditioning

    PubMed Central

    Zhang, Suyi; Mano, Hiroaki; Ganesh, Gowrishankar; Robbins, Trevor; Seymour, Ben

    2016-01-01

    Summary Pavlovian conditioning underlies many aspects of pain behavior, including fear and threat detection [1], escape and avoidance learning [2], and endogenous analgesia [3]. Although a central role for the amygdala is well established [4], both human and animal studies implicate other brain regions in learning, notably ventral striatum and cerebellum [5]. It remains unclear whether these regions make different contributions to a single aversive learning process or represent independent learning mechanisms that interact to generate the expression of pain-related behavior. We designed a human parallel aversive conditioning paradigm in which different Pavlovian visual cues probabilistically predicted thermal pain primarily to either the left or right arm and studied the acquisition of conditioned Pavlovian responses using combined physiological recordings and fMRI. Using computational modeling based on reinforcement learning theory, we found that conditioning involves two distinct types of learning process. First, a non-specific “preparatory” system learns aversive facial expressions and autonomic responses such as skin conductance. The associated learning signals—the learned associability and prediction error—were correlated with fMRI brain responses in amygdala-striatal regions, corresponding to the classic aversive (fear) learning circuit. Second, a specific lateralized system learns “consummatory” limb-withdrawal responses, detectable with electromyography of the arm to which pain is predicted. Its related learned associability was correlated with responses in ipsilateral cerebellar cortex, suggesting a novel computational role for the cerebellum in pain. In conclusion, our results show that the overall phenotype of conditioned pain behavior depends on two dissociable reinforcement learning circuits. PMID:26711494

  8. Incrementally Dissociating Syntax and Semantics

    ERIC Educational Resources Information Center

    Brennan, Jonathan R.

    2010-01-01

    A basic challenge for research into the neurobiology of language is understanding how the brain combines words to make complex representations. Linguistic theory divides this task into several computations including syntactic structure building and semantic composition. The close relationship between these computations, however, poses a strong…

  9. Intrinsic disorder accelerates dissociation rather than association.

    PubMed

    Umezawa, Koji; Ohnuki, Jun; Higo, Junichi; Takano, Mitsunori

    2016-08-01

    The intrinsically disordered protein (IDP) has distinct properties both physically and biologically: it often becomes folded when binding to the target and is frequently involved in signal transduction. The physical property seems to be compatible with the biological property where fast association and dissociation between IDP and the target are required. While fast association has been well studied, fueled by the fly-casting mechanism, the dissociation kinetics has received less attention. We here study how the intrinsic disorder affects the dissociation kinetics, as well as the association kinetics, paying attention to the interaction strength at the binding site (i.e., the quality of the "fly lure"). Coarse-grained molecular dynamics simulation of the pKID-KIX system, a well-studied IDP system, shows that the association rate becomes larger as the disorder-inducing flexibility that was imparted to the model is increased, but the acceleration is marginal and turns into deceleration as the quality of the fly lure is worsened. In contrast, the dissociation rate is greatly enhanced as the disorder is increased, indicating that intrinsic disorder serves for rapid signal switching more effectively through dissociation than association. Proteins 2016; 84:1124-1133. © 2016 Wiley Periodicals, Inc. PMID:27122223

  10. Ion-induced dissociation dynamics of acetylene

    SciTech Connect

    De, Sankar; Rajput, Jyoti; Roy, A.; Safvan, C. P.; Ghosh, P. N.

    2008-02-15

    We report on the results of dissociation dynamics of multiple charged acetylene molecules formed in collision with 1.2 MeV Ar{sup 8+} projectiles. Using the coincidence map, we can separate out the different dissociation pathways between carbon and hydrogen ionic fragments as well as complete two-body breakup events. From the measured slopes of the coincidence islands for carbon atomic fragments and theoretical values determined from the charge and momentum distribution of the correlated particles, we observe a diatom like behavior of the C-C charged complex during dissociation of multiply charged C{sub 2}H{sub 2}. We conclude that this behavior in breakup dynamics is a signature of sequentiality in dissociation of this multiply charged molecular species. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process of two- or many-body dissociation pathways. Kinetic energy release of different breakup channels are reported here and compared with values calculated from the pure Coulomb explosion model.

  11. Isotope separation by photoselective dissociative electron capture

    DOEpatents

    Stevens, Charles G. [Pleasanton, CA

    1978-08-29

    A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, .sup.235 UF.sub.6 is separated from a UF.sub.6 mixture by selective excitation followed by dissociative electron capture into .sup.235 UF.sub.5 - and F.

  12. Isotope separation by photoselective dissociative electron capture

    DOEpatents

    Stevens, C.G.

    1978-08-29

    Disclosed is a method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, [sup 235]UF[sub 6] is separated from a UF[sub 6] mixture by selective excitation followed by dissociative electron capture into [sup 235]UF[sub 5]- and F. 2 figs.

  13. Refractive index change in dissociating shocked benzene

    SciTech Connect

    Erskine, D.J.

    1994-06-01

    A calculation is made of the refractive index of a shocked solution of hydrocarbon species and spheroidal carbon particles that would be the dissociation products of benzene. The results is evaluated for benzene shocked to 15 GPa, both for an arbitrary endpoint distribution of products and reactant, and for a specific endpoint distribution suggested by a statistical-mechanical calculation. In the case of diamond particles, the refractive index is predicted to decrease by a small amount (from 1.96 to 1.75) as the dissociation proceeds. In the case of graphite particles of large oblateness, the refractive index could increase significantly through the dissociation (from 1.96 to 2.75 for infinitely oblate platelets). Thus the measurement of the time dependent refractive index through the dissociation of shocked benzene can indicate the morphology of the carbon particulates as well as the time scale for this reaction. We propose using the refractive index as a measure of completion of the dissociation reaction. This would allow a determination of the instantaneous amount of carbon in particulate form, information which is valuable in conjunction with Mie scattering experiments for example.

  14. Dissociation in virtual reality: depersonalization and derealization

    NASA Astrophysics Data System (ADS)

    Garvey, Gregory P.

    2010-01-01

    This paper looks at virtual worlds such as Second Life7 (SL) as possible incubators of dissociation disorders as classified by the Diagnostic and Statistical Manual of Mental Disorders, 4th Edition3 (also known as the DSM-IV). Depersonalization is where "a person feels that he or she has changed in some way or is somehow unreal." Derealization when "the same beliefs are held about one's surroundings." Dissociative Identity Disorder (DID), previously known as multiple personality disorder fits users of Second Life who adopt "in-world" avatars and in effect, enact multiple distinct identities or personalities (known as alter egos or alters). Select questions from the Structured Clinical Interview for Depersonalization (SCI-DER)8 will be discussed as they might apply to the user's experience in Second Life. Finally I would like to consider the hypothesis that rather than a pathological disorder, dissociation is a normal response to the "artificial reality" of Second Life.

  15. Electron Transfer Dissociation of Oligonucleotide Cations.

    PubMed

    Smith, Suncerae I; Brodbelt, Jennifer S

    2009-06-01

    Electron transfer dissociation (ETD) of multi-protonated 6 - 20-mer oligonucleotides and 12- and 14-mer duplexes is compared to collision activated dissociation (CAD). ETD causes efficient charge reduction of the multi-protonated oligonucleotides in addition to limited backbone cleavages to yield sequence ions of low abundance. Subsequent CAD of the charge-reduced oligonucleotides formed upon electron transfer, in a net process termed electron transfer collision activated dissociation (ETcaD), results in rich fragmentation in terms of w, a, z, and d products, with a marked decrease in the abundance of base loss ions and internal fragments. Complete sequencing was possible for nearly all oligonucleotides studied. ETcaD of an oligonucleotide duplex resulted in specific backbone cleavages, with conservation of weaker non-covalent bonds. PMID:20161288

  16. Psychotherapy and pharmacotherapy for patients with dissociative identity disorder.

    PubMed

    Gentile, Julie P; Dillon, Kristy S; Gillig, Paulette Marie

    2013-02-01

    There is a wide variety of what have been called "dissociative disorders," including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma report "dissociative" symptoms. Prevalence of dissociative disorders is unknown, but current estimates are higher than previously thought. This paper reviews clinical, phenomenological, and epidemiological data regarding diagnosis in general, and illustrates possible treatment interventions for dissociative identity disorder, with a focus on psychotherapy interventions and a review of current psychopharmacology recommendations as part of a comprehensive multidisciplinary treatment plan. PMID:23556139

  17. Swirling flow of a dissociated gas

    NASA Technical Reports Server (NTRS)

    Wolfram, W. R., Jr.; Walker, W. F.

    1975-01-01

    Most physical applications of the swirling flow, defined as a vortex superimposed on an axial flow in the nozzle, involve high temperatures and the possibility of real gas effects. The generalized one-dimensional swirling flow in a converging-diverging nozzle is analyzed for equilibrium and frozen dissociation using the ideal dissociating gas model. Numerical results are provided to illustrate the major effects and to compare with results obtained for a perfect gas with constant ratio of specific heats. It is found that, even in the case of real gases, perfect gas calculations can give a good estimate of the reduction in mass flow due to swirl.

  18. Dissociation of ultracold molecules with Feshbach resonances

    SciTech Connect

    Duerr, Stephan; Volz, Thomas; Rempe, Gerhard

    2004-09-01

    Ultracold molecules are associated from an atomic Bose-Einstein condensate by ramping a magnetic field across a Feshbach resonance. The reverse ramp dissociates the molecules. The kinetic energy released in the dissociation process is used to measure the widths of four Feshbach resonances in {sup 87}Rb. This method to determine the width works remarkably well for narrow resonances even in the presence of significant magnetic-field noise. In addition, a quasimonoenergetic atomic wave is created by jumping the magnetic field across the Feshbach resonance.

  19. Dissociation and recombination in an inhomogeneous gas

    NASA Astrophysics Data System (ADS)

    Kuščer, Ivan

    1991-09-01

    The system of Boltzmann equations of Ludwig and Heil for a dissociating gas mixture is reviewed and reformulated in terms of differential cross sections. For the purpose of Monte Carlo simulations, collision models of the type of Borgnakke and Larsen are proposed. In case of short-lived transient flows of molecular gases and at not too high temperatures, simulation of scattering collisions is expected to suffice; the distribution function of the dissociated particles can be evaluated afterwards by integration, and recombination can be ignored.

  20. Quantum Zeno control of coherent dissociation

    SciTech Connect

    Khripkov, C.; Vardi, A.

    2011-08-15

    We study the effect of dephasing on the coherent dissociation dynamics of an atom-molecule Bose-Einstein condensate. We show that when phase-noise intensity is strong with respect to the inverse correlation time of the stimulated process, dissociation is suppressed via a Bose enhanced quantum Zeno effect. This is complementary to the quantum Zeno control of phase-diffusion in a bimodal condensate by symmetric noise [Phys. Rev. Lett. 100, 220403 (2008)] in that the controlled process here is phase formation and the required decoherence mechanism for its suppression is purely phase noise.

  1. Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

    NASA Astrophysics Data System (ADS)

    Laporta, V.; Tennyson, J.; Celiberto, R.

    2016-02-01

    Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying \\text{X}{{}2}\\Pi resonance of CO-. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

  2. Double Dissociation between Reading and Spelling Deficits

    ERIC Educational Resources Information Center

    Moll, Kristina; Landerl, Karin

    2009-01-01

    In two studies dissociations between reading and spelling skills were examined. Study 1 reports equally high prevalence rates for isolated deficits in reading (7%) or spelling (6%) in a representative sample (N = 2,029) of German-speaking elementary school children. In Study 2, children with isolated deficits were presented with the same words to…

  3. Kinetic ion thermometers for electron transfer dissociation.

    PubMed

    Pepin, Robert; Tureček, František

    2015-02-19

    Peptide fragment ions of the z-type were used as kinetic ion thermometers to gauge the internal energy of peptide cation-radicals produced by electron transfer in the gas-phase. Electron transfer dissociation (ETD)-produced z2 ions containing the leucine residue, z2(Leu-Lys) and z2(Leu-Arg), were found to undergo spontaneous dissociation by loss of C3H7 that was monitored by time-resolved kinetic measurements on the time scale of the linear ion trap mass spectrometer. Kinetic modeling of the dissociations, including collisional cooling and product loss by neutralization, provided unimolecular rate constants for dissociation that were converted to the z ion internal energies using RRKM theory. The internal energy of z2(Leu-Lys) and z2(Leu-Arg) fragment ions was found to decrease with the increasing size of the precursor peptide ion, indicating vibrational energy partitioning between the ion and neutral fragments and ergodic behavior. The experimentally determined excitation in the peptide cation-radicals upon electron transfer (285-327 kJ mol(-1)) was found to be lower than that theoretically calculated from the reaction exothermicity. The reasons for this missing energy are discussed. PMID:25594857

  4. EVIDENCE FOR CO DISSOCIATION ON RHODIUM SURFACES

    SciTech Connect

    Castner, D.G.; Dubois, L.H.; Sexton, B.A.; Somorjai, G.A.

    1980-06-01

    Carbon monoxide adsorbs molecularly on rhodium surfaces at 300K, but if the rhodium samples are heated in the presence of carbon monoxide, there is evidence for carbon-oxygen bond breaking at step and/or defect sites. The effects of step and defect site density, subsurface oxygen concentration, and oxygen dissolution into the rhodium lattice on CO dissociation are discussed.

  5. Dissociative and double photoionization of CO2 from threshold to 90 A

    NASA Technical Reports Server (NTRS)

    Masuoka, T.; Samson, J. A. R.

    1979-01-01

    The molecular photoionization, dissociative photoionization and double photoionization cross sections for CO2 were measured from their onsets down to 90 A by using various combinations of mass spectrometers (a coincidence time-of-flight mass spectrometer and a magnetic mass spectrometer) and light sources (synchrotron radiation, and glow and spark discharge). It is concluded that the one broad peak and the three shoulders in the total adsorption cross section curve between 640 and 90 A are caused completely by dissociative ionization processes. Several peaks observed in the cross section curve for the total fragmentation CO(+)3, O(+) and C(+) are compared with those in the photoelectron spectrum reported for CO2.

  6. Multiphoton dissociation of electrosprayed megadalton-sized DNA ions in a charge-detection mass spectrometer.

    PubMed

    Doussineau, Tristan; Paletto, Pierre; Dugourd, Philippe; Antoine, Rodolphe

    2015-01-01

    Charge detection mass spectrometry in combination with a linear electrostatic ion trap coupled to a continuous wavelength infrared CO2 laser has been used to study the multiphoton dissociation of DNA macromolecular ions. Samples, with masses ranging from 2.23 to 31.5 MDa, include single strand circular M13mp18, double strand circular M13mp18, and double strand linear LambdaPhage DNA fragments. Their activation energies for unimolecular dissociation were determined. Activation energy values slightly increase as a function of the molecular weight. The most important result is the difference between the fragmentations observed for hybridized double-strands and dimers of single strands. PMID:25348472

  7. Electromagnetic dissociation of relativistic {sup 28}Si by nucleon emission

    SciTech Connect

    Sonnadara, U.J.

    1992-12-01

    A detailed study of the electromagnetic dissociation of {sup 28}Si by nucleon emission at E{sub lab}/A = 14.6 (GeV/nucleon was carried out with {sup 28}Si beams interacting on {sup 208}Pb). {sup 120}Sn. {sup 64}C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge Z{sub T} and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of {sup 28}Si {yields} p+{sup 27}Al and {sup 28}Si {yields} n+{sup 27}Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in {sup 28}Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear {sup 28}Si({sub {gamma},p}){sup 27}Al and {sup 28}Si({sub {gamma},n}){sup 27}Si. The possibilities of observing double giant dipole resonance excitations in {sup 28}Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  8. Electromagnetic dissociation of relativistic [sup 28]Si by nucleon emission

    SciTech Connect

    Sonnadara, U.J.

    1992-12-01

    A detailed study of the electromagnetic dissociation of [sup 28]Si by nucleon emission at E[sub lab]/A = 14.6 (GeV/nucleon was carried out with [sup 28]Si beams interacting on [sup 208]Pb). [sup 120]Sn. [sup 64]C targets. The measurements apparatus consists of detectors in the target area which measure the energy and charged multiplicity, and a forward spectrometer which measures the position, momentum and energy of the reaction fragments. The exclusive electromagnetic dissociation cross sections for decay channels having multiple nucleons in the final state have been measured which enables the selection of events produced in pure electromagnetic interactions. The measured cross sections agree well with previous measurements obtained for the removal of a few nucleons as well as with measurements on total charge removal cross sections from other experiments. The dependence of the integrated cross sections on the target charge Z[sub T] and the target mass AT confirms that for higher Z targets the excitation is largely electromagnetic. Direct measurements of the excitation energy for the electromagnetic dissociation of [sup 28]Si [yields] p+[sup 27]Al and [sup 28]Si [yields] n+[sup 27]Si have been obtained through a calculation of the invariant mass in kinematically, reconstructed events. The excitation energy spectrum for all targets peak near the isovector giant dipole resonance in [sup 28]Si. These distributions are well reproduced by combining the photon spectrum calculated using the Weizsaecker-Williams approximation with the experimental data on the photonuclear [sup 28]Si([sub [gamma],p])[sup 27]Al and [sup 28]Si([sub [gamma],n])[sup 27]Si. The possibilities of observing double giant dipole resonance excitations in [sup 28]Si have been investigated with cross section measurements as well as with excitation energy reconstruction.

  9. Experimental Dissociation of Methane Hydrates Through Depressurization

    NASA Astrophysics Data System (ADS)

    Borgfeldt, T.; Flemings, P. B.; Meyer, D.; You, K.

    2015-12-01

    We dissociated methane hydrates by stepwise depressurization. The initial hydrates were formed by injecting gas into a cylindrical sample of brine-saturated, coarse-grained sand at hydrate-stable conditions with the intention of reaching three-phase equilibrium. The sample was initially at 1°C with a pore pressure of 1775 psi and a salinity of 7 wt. % NaBr. The depressurization setup consisted of one pump filled with tap water attached to the confining fluid port and a second pump attached to the inlet port where the methane was injected. Depressurization was conducted over sixteen hours at a constant temperature of 1°C. The pore pressure was stepwise reduced from 1775 psi to atmospheric pressure by pulling known volumes of gas from the sample. After each extraction, we recorded the instantaneous and equilibrium pore pressure. 0.503 moles of methane were removed from the sample. The pore pressure decreased smoothly and nonlinearly with the cumulative gas withdrawn from the sample. We interpret that hydrate began to dissociate immediately with depressurization, and it continued to dissociate when the pressure decreased below the three-phase pressure for 1°C and 0 wt. % salinity. Two breaks in slope in the pressure vs. mass extracted data are bounded by smooth, nonlinear curves with differing slopes on either side. We attribute the breaks to dissociation of three zones of hydrate concentration. We created a box model to simulate the experimental behavior. For a 10% initial gas saturation (estimated from the hydrate formation experiment and based on mass conservation), an initial hydrate saturation of 55% is required to match the total methane extracted from the sample. Future experiments will be conducted over a longer timespan while monitoring hydrate dissociation with CT imaging throughout the process.

  10. Thermal dissociation behavior and dissociation enthalpies of methane-carbon dioxide mixed hydrates

    SciTech Connect

    Kwon, T.H.; Kneafsey, T.J.; Rees, E.V.L.

    2011-02-15

    Replacement of methane with carbon dioxide in hydrate has been proposed as a strategy for geologic sequestration of carbon dioxide (CO{sub 2}) and/or production of methane (CH{sub 4}) from natural hydrate deposits. This replacement strategy requires a better understanding of the thermodynamic characteristics of binary mixtures of CH{sub 4} and CO{sub 2} hydrate (CH{sub 4}-CO{sub 2} mixed hydrates), as well as thermophysical property changes during gas exchange. This study explores the thermal dissociation behavior and dissociation enthalpies of CH{sub 4}-CO{sub 2} mixed hydrates. We prepared CH{sub 4}-CO{sub 2} mixed hydrate samples from two different, well-defined gas mixtures. During thermal dissociation of a CH{sub 4}-CO{sub 2} mixed hydrate sample, gas samples from the head space were periodically collected and analyzed using gas chromatography. The changes in CH{sub 4}-CO{sub 2} compositions in both the vapor phase and hydrate phase during dissociation were estimated based on the gas chromatography measurements. It was found that the CO{sub 2} concentration in the vapor phase became richer during dissociation because the initial hydrate composition contained relatively more CO{sub 2} than the vapor phase. The composition change in the vapor phase during hydrate dissociation affected the dissociation pressure and temperature; the richer CO{sub 2} in the vapor phase led to a lower dissociation pressure. Furthermore, the increase in CO{sub 2} concentration in the vapor phase enriched the hydrate in CO{sub 2}. The dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate was computed by fitting the Clausius-Clapeyron equation to the pressure-temperature (PT) trace of a dissociation test. It was observed that the dissociation enthalpy of the CH{sub 4}-CO{sub 2} mixed hydrate lays between the limiting values of pure CH{sub 4} hydrate and CO{sub 2} hydrate, increasing with the CO{sub 2} fraction in the hydrate phase.

  11. Psychotherapy and Pharmacotherapy for Patients with Dissociative Identity Disorder

    PubMed Central

    Gentile, Julie P.; Dillon, Kristy S.

    2013-01-01

    There is a wide variety of what have been called “dissociative disorders,” including dissociative amnesia, dissociative fugue, depersonalization disorder, dissociative identity disorder, and forms of dissociative disorder not otherwise specified. Some of these diagnoses, particularly dissociative identity disorder, are controversial and have been questioned by many clinicians over the years. The disorders may be under-diagnosed or misdiagnosed, but many persons who have experienced trauma report “dissociative” symptoms. Prevalence of dissociative disorders is unknown, but current estimates are higher than previously thought. This paper reviews clinical, phenomenological, and epidemiological data regarding diagnosis in general, and illustrates possible treatment interventions for dissociative identity disorder, with a focus on psychotherapy interventions and a review of current psychopharmacology recommendations as part of a comprehensive multidisciplinary treatment plan. PMID:23556139

  12. Numerical simulation of the dissociation of I2 by O2 (1 Delta) in a two dimensional parallel jet

    NASA Astrophysics Data System (ADS)

    Miller, Jeffrey A.

    1989-03-01

    The thin-shear-layer equations are solved for a two dimensional parallel jet of molecular iodine in singlet delta oxygen freestream, to investigate the effect of mixing and water vapor on molecular iodine dissociation in Chemical Oxygen-Iodine Lasers (COIL). Predicting the dissociation of molecular iodine has been identified as the largest source of error in COIL performance modeling. Recent experimental and modeling experience have indicated that much of the problem may be due to the coupled iodine mixing and dissociation process. The numerical code was used to study the combined mixing and dissociation problem. Comparison of a set of 1-D premixed cases and 2-D jet cases with varying jet velocity ratios (and mixing rates) indicates that, imperfect mixing which results in initial regions of high iodine concentration leads to faster dissociation rates. High laser gain, however, does require efficient mixing. The results of both premixed and jet mixed cases with and without water vapor in the oxygen stream demonstrate the strong dependence of the dissociation efficiency (i.e., the penalty paid to dissociate iodine) on both the device geometry and operating conditions which challenges the wisdom of suing empirically determined efficiency factors to predict COIL performance.

  13. The H2 dissociation on the BN, AlN, BP and AlP nanotubes: a comparative study.

    PubMed

    Beheshtian, Javad; Soleymanabadi, Hamed; Kamfiroozi, Mohammad; Ahmadi, Ali

    2012-06-01

    The thermodynamic and kinetic feasibility of H(2) dissociation on the BN, AlN, BP and AlP zigzag nanotubes has been investigated theoretically by calculating the dissociation and activation energies. We determined the BN and AlP tubes to be inert toward H(2) dissociation, both thermodynamically and kinetically. The reactions are endothermic by 5.8 and 3 kcal mol(-1), exhibiting high activation energies of 38.8 and 30.6 kcal mol(-1), respectively. Our results indicated that H(2) dissociation is thermodynamically favorable on both PB and AlN nanotubes. However, in spite of the thermodynamic feasibility of H(2) dissociation on PB types, this process is kinetically unfavorable due to partly high activation energy. Generally, we concluded that among the four studied tubes, the AlN nanotube may be an appropriate model for H(2) dissociation process, from a thermodynamic and kinetic stand point. We also indicated that H(2) dissociation is not homolytic, rather it takes place via a heterolytic bond cleavage. In addition, a comparative study has been performed on the electrical and geometrical properties of the tubes. Our analysis showed that the electrical conductivity of tubes is as follows: BP>AlP>BN>AlN depending on how to combine the electron rich and electron poor atoms. PMID:21979405

  14. What contributes to predicting change in the treatment of dissociation: initial levels of dissociation, PTSD, or overall distress?

    PubMed

    Brand, Bethany L; Stadnik, Ryan

    2013-01-01

    Individuals with dissociative disorders (DDs) suffer from high levels of dissociation as well as posttraumatic stress disorder (PTSD) and general distress. No research has investigated how changes in dissociation relate to changes in other symptoms over the course of treatment in patients with DD. Using a prospective, naturalistic design, we collected reports of symptoms from a sample of therapists and their patients diagnosed with dissociative identity disorder or dissociative disorder not otherwise specified who participated in the Treatment Outcome of Patients with Dissociative Disorders study. The patients completed surveys at intake (Time 1) into the study and at 30-month follow-up (Time 4). We found that dissociative symptoms, including amnesia, depersonalization/derealization, and absorption, at the initial assessment of the study ("initial") were related to initial levels of PTSD and general distress and that changes in dissociative symptoms were related to changes in PTSD and general distress. Initial dissociation was a significant predictor of change in dissociation at 30 months when we controlled for length of time for follow-up, length of time practicing therapy, and length of time treating dissociative patients. Our results suggest that a reduction in dissociative symptoms in DD patients is associated with reductions in the overall severity of dissociative, posttraumatic stress, and distress symptoms. PMID:23627481

  15. Hydrogen Dissociation, Spillover, and Desorption from Cu-Supported Co Nanoparticles.

    PubMed

    Lewis, Emily A; Marcinkowski, Matthew D; Murphy, Colin J; Liriano, Melissa L; Sykes, E Charles H

    2014-10-01

    Co-Cu nanoparticles have recently been explored for Fischer-Tropsch synthesis (FTS) as a way to combine the long chain selectivity of Co with Cu's activity for alcohol formation in order to synthesize oxygenated transportation fuels. Depending on particle size, hydrogen dissociation can be a rate-determining step in cobalt-catalyzed FTS. To understand the fundamentals of uptake and release of hydrogen from the Co/Cu bimetallic system, we prepared well-defined Co nanoparticles on Cu(111). We demonstrate that hydrogen spills over from dissociation sites on the Co nanoparticles to the Cu(111) surface via the Co-Cu interface and that desorption of H occurs at a temperature that is lower than from Co or Cu alone, which we attribute to the Co-Cu interface sites. From this data, we have constructed an energy landscape for the facile dissociation, spillover, and desorption of hydrogen on the Co-Cu bimetallic system. PMID:26278448

  16. A molecular dynamics study of melting and dissociation of tungsten nanoparticles

    SciTech Connect

    Li, Min; Wang, Jun; Fu, Baoqin; Hou, Qing

    2015-12-15

    Molecular dynamics simulations were conducted to study the melting and dissociation of free tungsten nanoparticles. For the various interatomic potentials applied, the melting points of the tungsten nanoparticles increased with increasing nanoparticle diameter. Combining these results with the melting point of bulk tungsten in the experiment, the melting point of nanoparticles with diameters ranging from 4 to 12 nm could be determined. As the temperature increases, free nanoparticles are subject to dissociation phenomena. The dissociation rate was observed to follow Arrhenius behavior, and the Meyer–Neldel rule was obeyed. These results are useful in understanding the behavior of tungsten dust generated in nuclear fusion devices as well as for the preparation, formation, and application of tungsten powders.

  17. A molecular dynamics study of melting and dissociation of tungsten nanoparticles

    NASA Astrophysics Data System (ADS)

    Li, Min; Wang, Jun; Fu, Baoqin; Hou, Qing

    2015-12-01

    Molecular dynamics simulations were conducted to study the melting and dissociation of free tungsten nanoparticles. For the various interatomic potentials applied, the melting points of the tungsten nanoparticles increased with increasing nanoparticle diameter. Combining these results with the melting point of bulk tungsten in the experiment, the melting point of nanoparticles with diameters ranging from 4 to 12 nm could be determined. As the temperature increases, free nanoparticles are subject to dissociation phenomena. The dissociation rate was observed to follow Arrhenius behavior, and the Meyer-Neldel rule was obeyed. These results are useful in understanding the behavior of tungsten dust generated in nuclear fusion devices as well as for the preparation, formation, and application of tungsten powders.

  18. Comparison of vibration dissociation coupling and radiative heat transfer models for AOTV/AFE flowfields

    NASA Technical Reports Server (NTRS)

    Carlson, Leland A.; Bobskill, Glenn J.; Greendyke, Robert B.

    1988-01-01

    A series of detailed studies comparing various vibration dissociation coupling models, reaction systems and rates, and radiative heating models has been conducted for the nonequilibrium stagnation region of an AFE/AOTV vehicle. Atomic and molecular nonequilibrium radiation correction factors have been developed and applied to various absorption coefficient step models, and a modified vibration dissociation coupling model has been shown to yield good vibration/electronic temperature and concentration profiles. While results indicate sensitivity to the choice of vibration dissociation coupling model and to the nitrogen electron impact ionization rate, by proper combinations accurate flowfield and radiative heating results can be obtained. These results indicate that nonequilibrium effects significantly affect the flowfield and the radiative heat transfer. However, additional work is needed in ionization chemistry and absorption coefficient modeling.

  19. Signatures of bond formation and bond scission dynamics in dissociative electron attachment to methane.

    PubMed

    Douguet, N; Slaughter, D S; Adaniya, H; Belkacem, A; Orel, A E; Rescigno, T N

    2015-10-14

    We present a combined experimental and theoretical investigation of the dynamics and angular dependence of dissociative electron attachment to methane. We show that a triply degenerate (T2) Feshbach resonance is responsible for the broad 10 eV dissociation peak in methane. This resonance alone is shown to correlate asymptotically to the various dissociation channels observed experimentally. The molecular-frame entrance amplitude for electron attachment is calculated for each component of the threefold degenerate resonance. By investigating the topology of the anion potential energy surfaces, we deduce the main pathways to two- and three-body breakup channels involving both bond scission and bond formation. The computed fragment angular distributions reproduce the main trends of the experimental measurements. PMID:26371546

  20. Coherent dissociation of relativistic {sup 9}C nuclei in nuclear track emulsion

    SciTech Connect

    Krivenkov, D. O.; Artemenkov, D. A.; Bradnova, V.; Kattabekov, R. R.; Kondratieva, N. V.; Mamatkulov, K. Z.; Malakhov, A. I.; Rukoyatkin, P. A.; Rusakova, V. V.; Stanoeva, R.; Zarubin, P. I.; Zarubina, I. G.; Haiduc, M.; Kharlamov, S. P.; Orlova, G. I.; Peresadko, N. G.; Polukhina, N. G.; Moiseenko, A. A.; Sarkisyan, V. R.; Vokal, S.

    2010-04-30

    For the first time nuclear track emulsion is exposed to relativistic {sup 9}C nuclei. A systematic pattern of the distributions of charge combinations of fragments in the peripheral interactions of {sup 9}C nuclei in a nuclear track emulsion has been obtained. The main conclusion is that the contribution of the channel {sup 9}C->{sup 8}B+p and {sup 9}C->{sup 7}Be+2p is most important in events that do not involve the production of target-nucleus fragments or mesons (coherent dissociation). It can be concluded that in the peripheral {sup 9}C dissociation the picture hitherto obtained for {sup 8}B and {sup 7}Be with the addition of one or two protons, respectively, is reproduced. Three coherent dissociation events {sup 9}C->3{sup 3}He accompanied by neither target fragments of the nucleus target nor charged mesons are identified.

  1. The dissociation between subjective workload and performance A multiple resource approach

    NASA Technical Reports Server (NTRS)

    Wickens, C. D.; Yeh, Y.-Y.

    1983-01-01

    A theory of the dissociation between subjective measures of mental workload and performance is described. The theory proposes that subjective measures are heavily driven by the number of tasks or task elements that a subject must perform concurrently. However they are relatively less sensitive to whether these tasks compete for common or separate resources, and to the difficulty of a single task, particularly if this difficulty is related to response factors. Performance, on the other hand, is particularly influenced by single task difficulty of both a perceptual and response nature and by resource competition between tasks. A set of three experiments are described to examine the dissociation between subjective difficulty measures and performance. These experiments employ different combinations of three tasks: tracking, memory search, and a simulated air traffic control problem. The results supported all forms of dissociation predicted by the theory and the implications of results to workload measurement are discussed.

  2. Surface induced dissociation yields substructure of Methanosarcina thermophila 20S proteasome complexes

    PubMed Central

    Ma, Xin; Loo, Joseph A.; Wysocki, Vicki H.

    2015-01-01

    Native mass spectrometry (MS) and surface induced dissociation (SID) have been applied to study the stoichiometry and quaternary structure of non-covalent protein complexes. In this study, Methanosarcina thermophila 20S proteasome, which consists of four stacked heptameric rings (α7β7β7α7 symmetry), has been selected to explore the SID dissociation pattern of a complicated stacked ring protein complex. SID produces both α and β subunits while collision induced dissociation (CID) produces only highly charged α subunit. In addition, the charge reduced 20S proteasome produces the α7β7 fragment, reflecting the stacked ring topology of the complex. The combination of SID and charge reduction is shown to be a powerful tool for the study of protein complex structure. PMID:26005366

  3. Revealing Dissociative Electron Attachment Dynamics in Polyatomic Molecules Using Momentum Imaging Experiments and Electron Scattering Calculations

    NASA Astrophysics Data System (ADS)

    Belkacem, Ali; Slaughter, Daniel

    2015-05-01

    Understanding electron-driven chemical reactions is important for improving a variety of technological applications such as materials processing and the important role they play in the radiation damage in bulk matter. Furthermore, dissociative electron attachment often exhibits site-selective bond cleavage, which holds promise for prediction and precise control of electron-driven chemical reactions. Recent dynamical studies of these reactions have demonstrated that an understanding of anion dissociation dynamics beyond simple one-dimensional models is crucial in interpreting the measured fragment angular distributions. We combine ion fragment momentum imaging experiments with electron attachment entrance amplitude calculations to interrogate the non-Born-Oppenheimer dynamics of dissociative electron attachment in polyatomic molecules. We will report recent experimental developments in molecules of technological interest including methanol, methane and uracil. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  4. Kinetics of Propargyl Radical Dissociation.

    PubMed

    Klippenstein, Stephen J; Miller, James A; Jasper, Ahren W

    2015-07-16

    Due to the prominent role of the propargyl radical for hydrocarbon growth within combustion environments, it is important to understand the kinetics of its formation and loss. The ab initio transition state theory-based master equation method is used to obtain theoretical kinetic predictions for the temperature and pressure dependence of the thermal decomposition of propargyl, which may be its primary loss channel under some conditions. The potential energy surface for the decomposition of propargyl is first mapped at a high level of theory with a combination of coupled cluster and multireference perturbation calculations. Variational transition state theory is then used to predict the microcanonical rate coefficients, which are subsequently implemented within the multiple-well multiple-channel master equation. A variety of energy transfer parameters are considered, and the sensitivity of the thermal rate predictions to these parameters is explored. The predictions for the thermal decomposition rate coefficient are found to be in good agreement with the limited experimental data. Modified Arrhenius representations of the rate constants are reported for utility in combustion modeling. PMID:25871530

  5. Conditional dissociation as a punishment mechanism in the evolution of cooperation

    NASA Astrophysics Data System (ADS)

    Qu, Xinglong; Zhou, Changli; Cao, Zhigang; Yang, Xiaoguang

    2016-05-01

    Recent studies show that conditional dissociation, a.k.a. post-interaction partner-refusal, can promote the emergence and stability of cooperation. However, in most of these studies, players' strategies are restricted to pure ones, which is obviously inconsistent with many biological and economic situations. Another concern with line of these studies is that conditional dissociation is often combined with other mechanisms. These mechanisms may favor cooperation per se, leaving it unclear whether conditional dissociation is indeed a key factor. In this paper, we study a clean model, pruning all the factors other than conditional dissociation that may favor cooperation. We find that conditional dissociation, which could be viewed as a variant of peer punishment, does promote cooperation, no matter whether mixed strategies are allowed or not. This confirms the previous findings in the literature. In addition, compared with the pure strategy scenario, cooperators are less competitive when mixed strategies are allowed. Our main finding is supported by both the numerical simulations and the theoretical analysis of Neutrally Stable Strategy. We also find that cooperative behavior is favored when waiting time and/or the population's lifespan are longer.

  6. Dissociation of acetaldehyde in intense laser field: Coulomb explosion or field-assisted dissociation?

    NASA Astrophysics Data System (ADS)

    Elshakre, Mohamed E.; Gao, Lirong; Tang, Xiaoping; Wang, Sufan; Shu, Yafei; Kong, Fanao

    2003-09-01

    Dissociation of acetaldehyde in moderate strong laser field of 1013-1014W/cm2 was investigated. Singly charged parent ion CH3CHO+ and fragmental ions CH3+, CHO+, C2H4+, O+, CH2CHO+, and H+ were produced by 800 nm laser of 100 fs pulse duration and recorded by time-of-flight mass spectrometer. The CH3+ fragment further dissociated to CH2+, CH+, and C+ ions at higher intensity. Ab initio calculated results show that the singly-, doubly-, and triply charged parent ions are stable. So, the dissociation mechanism was not due to Coulomb explosion of multicharged ion. A field-assisted dissociation (FAD) theory, which assumes that only one bond undergoes dissociation while the rest of the molecular geometry stays unchanged, was employed to treat the dissociation dynamics. Accordingly, the dressed potential energy surfaces of the ground state for the parent and the fragment ions were calculated. Corresponding quasiclassical trajectory calculations show that the bond ruptures take place in the order of C-C, C-O, and C-H, agreeing with the observation. The observed angular dependence and charge distribution of the product ions can also be interpreted by the FAD theory.

  7. Does phasic trauma treatment make patients with dissociative identity disorder treatment more dissociative?

    PubMed

    Brand, Bethany; Loewenstein, Richard J

    2014-01-01

    Proponents of the iatrogenic model of the etiology of dissociative identity disorder (DID) have expressed concern that treatment focused on direct engagement and interaction with dissociated self-states harms DID patients. However, empirical data have shown that this type of DID treatment is beneficial. Analyzing data from the prospective Treatment of Patients With Dissociative Disorders (TOP DD) Study, we test empirically whether DID treatment is associated with clinically adverse manifestations of dissociated self-states: acting so differently that one feels like different people, hearing voices, and dissociative amnesia. We show that, over the course of the study, there were significant decreases in feeling like different people and hearing voices. These results indicate that this form of DID treatment does not lead to symptomatic worsening in these dimensions, as predicted by the iatrogenic model. Indeed, treatment provided by TOP DD therapists reduced, rather than increased, the extent to which patients experienced manifestations of pathological dissociation. Because severe symptomatology and impairment are associated with DID, iatrogenic harm may come from depriving DID patients of treatment that targets DID symptomatology. PMID:24377972

  8. In-Vacuum Dissociator for Atomic-Hydrogen Masers

    NASA Technical Reports Server (NTRS)

    Vessot, R. F.

    1987-01-01

    Thermal control and vacuum sealing achieved while contamination avoided. Simple, relatively inexpensive molecular-hydrogen dissociator for atomic-hydrogen masers used on Earth or in vacuum of space. No air cooling required, and absence of elastomeric O-ring seals prevents contamination. In-vacuum dissociator for atomic hydrogen masers, hydrogen gas in glass dissociator dissociated by radio-frequency signal transmitted from surrounding 3-turn coil. Heat in glass conducted away by contacting metal surfaces.

  9. 21 CFR 886.1910 - Spectacle dissociation test system.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Spectacle dissociation test system. 886.1910... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1910 Spectacle dissociation test system. (a) Identification. A spectacle dissociation test system is an AC-powered or...

  10. 21 CFR 886.1910 - Spectacle dissociation test system.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Spectacle dissociation test system. 886.1910... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1910 Spectacle dissociation test system. (a) Identification. A spectacle dissociation test system is an AC-powered or...

  11. 21 CFR 886.1910 - Spectacle dissociation test system.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Spectacle dissociation test system. 886.1910... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1910 Spectacle dissociation test system. (a) Identification. A spectacle dissociation test system is an AC-powered or...

  12. 21 CFR 886.1910 - Spectacle dissociation test system.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Spectacle dissociation test system. 886.1910... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1910 Spectacle dissociation test system. (a) Identification. A spectacle dissociation test system is an AC-powered or...

  13. Development, Reliability, and Validity of a Child Dissociation Scale.

    ERIC Educational Resources Information Center

    Putnam, Frank W.; And Others

    1993-01-01

    Evaluation of the Child Dissociative Checklist found it to be a reliable and valid observer report measure of dissociation in children, including sexually abused girls and children with dissociative disorder and with multiple personality disorder. The checklist, which is appended, is intended as a clinical screening instrument and research measure…

  14. Speech-Language Dissociations, Distractibility, and Childhood Stuttering

    PubMed Central

    Conture, Edward G.; Walden, Tedra A.; Lambert, Warren E.

    2015-01-01

    Purpose This study investigated the relation among speech-language dissociations, attentional distractibility, and childhood stuttering. Method Participants were 82 preschool-age children who stutter (CWS) and 120 who do not stutter (CWNS). Correlation-based statistics (Bates, Appelbaum, Salcedo, Saygin, & Pizzamiglio, 2003) identified dissociations across 5 norm-based speech-language subtests. The Behavioral Style Questionnaire Distractibility subscale measured attentional distractibility. Analyses addressed (a) between-groups differences in the number of children exhibiting speech-language dissociations; (b) between-groups distractibility differences; (c) the relation between distractibility and speech-language dissociations; and (d) whether interactions between distractibility and dissociations predicted the frequency of total, stuttered, and nonstuttered disfluencies. Results More preschool-age CWS exhibited speech-language dissociations compared with CWNS, and more boys exhibited dissociations compared with girls. In addition, male CWS were less distractible than female CWS and female CWNS. For CWS, but not CWNS, less distractibility (i.e., greater attention) was associated with more speech-language dissociations. Last, interactions between distractibility and dissociations did not predict speech disfluencies in CWS or CWNS. Conclusions The present findings suggest that for preschool-age CWS, attentional processes are associated with speech-language dissociations. Future investigations are warranted to better understand the directionality of effect of this association (e.g., inefficient attentional processes → speech-language dissociations vs. inefficient attentional processes ← speech-language dissociations). PMID:26126203

  15. Cognitive Processes in Dissociation: Comment on Giesbrecht et al. (2008)

    ERIC Educational Resources Information Center

    Bremner, J. Douglas

    2010-01-01

    In their recent review "Cognitive Processes in Dissociation: An Analysis of Core Theoretical Assumptions," published in "Psychological Bulletin", Giesbrecht, Lynn, Lilienfeld, and Merckelbach (2008) have challenged the widely accepted trauma theory of dissociation, which holds that dissociative symptoms are caused by traumatic stress. In doing so,…

  16. MDMA, cannabis, and cocaine produce acute dissociative symptoms.

    PubMed

    van Heugten-Van der Kloet, Dalena; Giesbrecht, Timo; van Wel, Janelle; Bosker, Wendy M; Kuypers, Kim P C; Theunissen, Eef L; Spronk, Desirée B; Jan Verkes, Robbert; Merckelbach, Harald; Ramaekers, Johannes G

    2015-08-30

    Some drugs of abuse may produce dissociative symptoms, but this aspect has been understudied. We explored the dissociative potential of three recreational drugs (3,4-methylenedioxymethamphetamine (MDMA), cannabis, and cocaine) during intoxication and compared their effects to literature reports of dissociative states in various samples. Two placebo-controlled studies were conducted. In Study 1 (N=16), participants received single doses of 25, 50, and 100 mg of MDMA, and placebo. In Study 2 (N=21), cannabis (THC 300 µg/kg), cocaine (HCl 300 mg), and placebo were administered. Dissociative symptoms as measured with the Clinician-Administered Dissociative States Scale (CADSS) significantly increased under the influence of MDMA and cannabis. To a lesser extent, this was also true for cocaine. Dissociative symptoms following MDMA and cannabis largely exceeded those observed in schizophrenia patients, were comparable with those observed in Special Forces soldiers undergoing survival training, but were lower compared with ketamine-induced dissociation. Cocaine produced dissociative symptoms that were comparable with those observed in schizophrenia patients, but markedly less than those in Special Forces soldiers and ketamine users. Thus, MDMA and cannabis can produce dissociative symptoms that resemble dissociative pathology. The study of drug induced dissociation is important, because it may shed light on the mechanisms involved in dissociative psychopathology. PMID:26003508

  17. Cognitive Processes in Dissociation: An Analysis of Core Theoretical Assumptions

    ERIC Educational Resources Information Center

    Giesbrecht, Timo; Lilienfield, Scott O.; Lynn, Steven Jay; Merckelbach, Harald

    2008-01-01

    Dissociation is typically defined as the lack of normal integration of thoughts, feelings, and experiences into consciousness and memory. The present article critically evaluates the research literature on cognitive processes in dissociation. The authors' review indicates that dissociation is characterized by subtle deficits in neuropsychological…

  18. Rate coefficients for dissociative attachment and resonant electron-impact dissociation involving vibrationally excited O{sub 2} molecules

    SciTech Connect

    Laporta, V.; Celiberto, R.; Tennyson, J.

    2014-12-09

    Rate coefficients for dissociative electron attachment and electron-impact dissociation processes, involving vibrationally excited molecular oxygen, are presented. Analytical fits of the calculated numerical data, useful in the applications, are also provided.

  19. Theoretical dissociation energies for ionic molecules

    NASA Technical Reports Server (NTRS)

    Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

    1986-01-01

    Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

  20. Dynamics of Dissociative Electron Attachment to Methane

    NASA Astrophysics Data System (ADS)

    Rescigno, T. N.; Douguet, N.; Fonseca, S.; Orel, A. E.; Slaughter, D. S.; Belkacem, A.

    2015-05-01

    We present the results of a theoretical ad experimental study of dissociative electron attachment (DEA) to CH4. The total DEA cross section is dominated by a single broad peak centered near 10 eV, leading predominantly to H-/CH4 and CH2-/CH4dissociation channels. We will present evidence that both of these ion channels result from excitation of a triply degenerate Feshbach resonance (doubly excited negative ion state) of 2T2 symmetry whose parent is the lowest excited triplet state of the neutral molecule. We will present calculated angular distributions based on analysis of the entrance amplitudes obtained from the results of complex Kohn scattering calculations along with experimentally measured angular distributions obtained using the COLTRIMS method. Work performed under the auspices of the US DOE by the LBNL and supported by the U.S. DOE Office of Basic Energy Sciences, Division of Chemical Sciences.

  1. Vibrational relaxation and dissociation in nitrogen

    NASA Technical Reports Server (NTRS)

    Varghese, Philip L.; Gonzales, David A.

    1991-01-01

    Calculations of the vibrational and dissociation transition probabilities are made for N2-N2 and N2-N collisions by means of a semiclassical N-state approximation. The flaws in previous techniques are reviewed, with special attention given to the prediction of overtones. The method presented ignores the effects of molecular rotation and employs a revised extended Rydberg intermolecular potential to describe diatom-diatom and diatom-atom collisions. The collision velocities investigated exhibit probabilities of less than unity by means of the N-state method. The continuum is quantized to treat dissociation, and the collision results demonstrate probability enhancements for V-V-T transitions in both bound-bound and bound-free transitions. The technique is of particular interest for the theoretical modeling of reentry flows such as those encountered in aerobraking maneuvers.

  2. The dissociation energy of N2

    NASA Technical Reports Server (NTRS)

    Almloef, Jan; Deleeuw, Bradley J.; Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Siegbahn, Per

    1989-01-01

    The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

  3. Vibration dissociation coupling in nonequilibrium flows

    NASA Technical Reports Server (NTRS)

    Candler, Graham V.

    1992-01-01

    The final report on research between North Carolina State University and the NASA Ames Research Center is presented. The research was aimed at using the Schwartz, Slawsky, Herzfeld (SSH) theory to simulate the vibrational relaxation of nitrogen molecules undergoing dissociation or recombination over a wide range of conditions. The results of these simulations were then treated as exact, and they were used to develop a model for the coupled vibration-dissociation process. This new model is simple enough to be used in computational fluid dynamics codes, but still captures the physics of the complex process. The model is used to simulate the flow over typical geometries to test it and to determine how much impact it has on the flow field. The key elements of this research are summarized.

  4. Fluid hydrogen at high density - Pressure dissociation

    NASA Technical Reports Server (NTRS)

    Saumon, Didier; Chabrier, Gilles

    1991-01-01

    A model for the Helmholtz free energy of fluid hydrogen at high density and high temperature is developed. This model aims at describing both pressure and temperature dissociation and ionization and bears directly on equations of state of partially ionized plasmas, as encountered in astrophysical situations and high-pressure experiments. This paper focuses on a mixture of hydrogen atoms and molecules and is devoted to the study of the phenomenon of pressure dissociation at finite temperatures. In the present model, the strong interactions are described with realistic potentials and are computed with a modified Weeks-Chandler-Andersen fluid perturbation theory that reproduces Monte Carlo simulations to better than 3 percent. Theoretical Hugoniot curves derived from the model are in excellent agreement with experimental data.

  5. The charmonium dissociation in an "anomalous wind"

    NASA Astrophysics Data System (ADS)

    Sadofyev, Andrey V.; Yin, Yi

    2016-01-01

    We study the charmonium dissociation in a strongly coupled chiral plasma in the presence of magnetic field and axial charge imbalance. This type of plasma carries "anomalous flow" induced by the chiral anomaly and exhibits novel transport phenomena such as chiral magnetic effect. We found that the "anomalous flow" would modify the charmonium color screening length by using the gauge/gravity correspondence. We derive an analytical expression quantifying the "anomalous flow" experienced by a charmonium for a large class of chiral plasma with a gravity dual. We elaborate on the similarity and qualitative difference between anomalous effects on the charmonium color screening length which are model-dependent and those on the heavy quark drag force which are fixed by the second law of thermodynamics. We speculate on the possible charmonium dissociation induced by the chiral anomaly in heavy ion collisions.

  6. Dissociative Disorders: Between Neurosis and Psychosis

    PubMed Central

    Devillé, C.; Moeglin, C.; Sentissi, O.

    2014-01-01

    Dissociative disorders are a set of disorders defined by a disturbance affecting functions that are normally integrated with a prevalence of 2.4 percent in industrialised countries. These disorders are often poorly diagnosed or misdiagnosed because of sharing common clinical features with psychotic disorders, but requiring a very different trajectory of care. Repeated clinical situations in a crisis centre in Geneva provided us with a critical overview of current evidence of knowledge in clinical and etiopathological field about dissociative disorders. Because of their multiple expressions and the overlap with psychotic disorders, we focused on the clinical aspects using three different situations to better understand their specificity and to extend our thinking to the relevance of terms “neurosis” and “psychosis.” Finally, we hope that this work might help physicians and psychiatrists to become more aware of this complex set of disorders while making a diagnosis. PMID:25405051

  7. On the dissociation pathways of nitrobenzene

    NASA Astrophysics Data System (ADS)

    Kosmidis, C.; Ledingham, K. W. D.; Clark, A.; Marshall, A.; Jennings, R.; Sander, J.; Singhal, R. P.

    1994-08-01

    The fragmentation of nitrobenzene has been studied in the wavelength range 225-275 nm using a single dye laser, frequency doubled, in conjunction with a time-of-flight (TOF) mass spectrometer. The parent (C6H5NO2+), nitrosobenzene (C6H5NO+), phenoxy (C6H5O+) and phenyl (C6H5+) ions were all observed in addition to many other lighter daughter fragments. The formation of the nitrobenzene, phenoxy and phenyl ions are all explained invoking pathways where dissociation of the parent molecule from an excited state takes place first, followed by ionization after the absorption of further photons (DI) by the fragmented neutrals. Ionization of the parent molecule to states which are dissociative (ID) can explain the increase in the production of phenyl ions at wavelengths shorter than 230 nm.

  8. The charmonium dissociation in an ''anomalous wind''

    DOE PAGESBeta

    Sadofyev, Andrey V.; Yin, Yi

    2016-01-11

    We study the charmonium dissociation in a strongly coupled chiral plasma in the presence of magnetic field and axial charge imbalance. This type of plasma carries "anomalous flow" induced by the chiral anomaly and exhibits novel transport phenomena such as chiral magnetic effect. We found that the "anomalous flow" would modify the charmonium color screening length by using the gauge/gravity correspondence. We derive an analytical expression quantifying the "anomalous flow" experienced by a charmonium for a large class of chiral plasma with a gravity dual. We elaborate on the similarity and it qualitative difference between anomalous effects on the charmoniummore » color screening length which are model-dependent and those on the heavy quark drag force which are fixed by the second law of thermodynamics. As a result, we speculate on the possible charmonium dissociation induced by the chiral anomaly in heavy ion collisions.« less

  9. Dissociative Recombination Dynamics of the Ozone Cation

    SciTech Connect

    Zhaunerchyk, Vitali; Geppert, W.; sterdahl, F.; Larsson, Mats; Thomas, R. D.; Bahati Musafiri, Eric; Bannister, Mark E; Fogle, Mark R.; Vane, C Randy

    2008-02-01

    The dissociative recombination of the ozone cation has been studied at the heavy-ion storage ring CRYRING. The total cross section and branching fractions have been measured. The cross section from {approx}0eV to 0.2 eV follows a nearly E{sup -1} dependence, which was theoretically predicted to be a characteristic of the direct dissociative recombination mechanism. The thermal rate coefficient has been deduced from the cross section to be 7.37x10{sup -7}(T/300){sup -0.55}cm{sup 3}s{sup -1}. The branching fraction analysis carried out at {approx}0eV interaction energy has shown a strong propensity (94%) to dissociate through the three-body channel. Due to the overwhelming dominance of this channel it has been investigated in more detail. Of the six energetically available three-body pathways only three are significantly populated, such that the production of O(S1) is highly unfavored and all atomic oxygen fragments are predominantly formed in P3 and D1 states. Analysis of the breakup geometries has been performed by means of the Dalitz plot. It is observed that the molecules dissociating through the O(P3)+O(P3)+O(P3) and O(P3)+O(P3)+O(D1) channels have an open linear geometry where the cleavage of two valence bonds occurs preferentially in unison, while the O(P3)+O(D1)+O(D1) breakup might proceed partly through a sequential mechanism.

  10. The Bond Dissociation Energies of 1-Butene

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

    1994-01-01

    The bond dissociation energies of 1-butene and several calibration systems are computed using the G2(MP2) approach. The agreement between the calibration systems and experiment is very good. The computed values for 1-butene are compared with calibration systems and the agreement between the computed results for 1-butene and the "rule of thumb" values from the smaller systems is remarkably good.

  11. The infrared multiphoton dissociation of three nitrolkanes

    NASA Astrophysics Data System (ADS)

    Wodtke, A. M.; Hintsa, E. J.; Lee, Y. T.

    1986-01-01

    Infrared multiphoton dissociation in a molecular beam has been studied in order to elucidate the collision free, 'thermal' chemistry and dynamics of nitromethane, nitroethane and 2-nitropropane. The isomerization of CH3NO2 to CH3ONO was observed by detecting the CH3O and NO products from the dissociation of the very internally hot, isomerized nitromethane. A novel application of RRKM theory was used to estimate the barrier height to isomerization at 55.5 kcal/mol. The barrier height determination method was tested and found to give excellent results by applying it to the determintaion of the barrier height to HONO elimination from nitroethane, a value which is well known from activation energy measurements. The method was then applied to the case of HONO elimination from 2-nitropropane and it appears that there is good to believe that the barrier height is 3-5 kcal/mol lower in 2-nitropropane than in nitroethane. The success of this method for determining barrier heights shows how a microscopic molecular beam experiment, using infrared multiphoton dissociation where the concept of temperature has no place, can be quantitatively related to pyrolysis experiments which are conducted under collisional, thermal conditions and measure phenomenological quantities such as activation energies.

  12. Regional dissociated heterochrony in multivariate analysis.

    PubMed

    Mitteroecker, P; Gunz, P; Weber, G W; Bookstein, F L

    2004-12-01

    Heterochrony, the classic framework to study ontogeny and phylogeny, in essence relies on a univariate concept of shape. Though principal component plots of multivariate shape data seem to resemble classical bivariate allometric plots, the language of heterochrony cannot be translated directly into general multivariate methodology. We simulate idealized multivariate ontogenetic trajectories and demonstrate their behavior in principal component plots in shape space and in size-shape space. The concept of "dissociation", which is conventionally regarded as a change in the relationship between shape change and size change, appears to be algebraically the same as regional dissociation - the variation of apparent heterochrony by region. Only if the trajectories of two related species lie along exactly the same path in shape space can the classic terminology of heterochrony apply so that pure dissociation of size change against shape change can be detected. We demonstrate a geometric morphometric approach to these issues using adult and subadult crania of 48 Pan paniscus and 47 P. troglodytes. On each specimen we digitized 47 landmarks and 144 semilandmarks on ridge curves and the external neurocranial surface. The relation between these two species' growth trajectories is too complex for a simple summary in terms of global heterochrony. PMID:15646279

  13. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

    dos Santos, S. Fonseca; Ngassam, V.; Orel, A. E.; Larson, Å.

    2016-08-01

    The direct and indirect mechanisms of dissociative recombination of N2H+ are theoretically studied. At low energies, the electron capture is found to be driven by recombination into bound Rydberg states, while at collision energies above 0.1 eV, the direct capture and dissociation along electronic resonant states becomes important. Electron-scattering calculations using the complex Kohn variational method are performed to obtain the scattering matrix as well as energy positions and autoionization widths of resonant states. Potential-energy surfaces of electronic bound states of N2H and N2H+ are computed using structure calculations with the multireference configuration interaction method. The cross section for the indirect mechanism is calculated using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Here vibrational excitations of the ionic core from v =0 to v =1 and v =2 for all three normal modes are considered and autoionization is neglected. The cross section for the direct dissociation along electronic resonant states is computed with wave-packet calculations using the multiconfiguration time-dependent Hartree method, where all three internal degrees of freedom are considered. The calculated cross sections are compared to measurements.

  14. Kinetics of single DNA hairpin dissociation

    NASA Astrophysics Data System (ADS)

    Rogers, William; Crocker, John

    2010-03-01

    Over the past decade, groups have used a variety of single molecule techniques to study the unfolding and unbinding of nucleic acids, proteins and other biomolecules. While some experiments on the dissociation of nucleic acids find exponential lifetime distributions, as expected for a process governed by a single rate-limiting pathway, other experiments find nonexponential lifetime distributions. In our work, we address this discrepancy by probing the force dependence of a single DNA hairpin under thermal dissociation. We use a scanning line optical tweezers instrument to measure the bound lifetimes of two DNA-coated microspheres under negligible applied tension. The two microspheres share a user-specified potential along the scan direction and are strongly confined in the perpendicular dimensions. The trapping laser intensity is modulated synchronously with a resonant scanning mirror to null all optical contributions to the pair interaction potential near contact. In addition, the laser polarization can be rotated to produce a continuously adjustable optical repulsion, allowing the instrument to double as a passive force clamp over a modest range of applied tensions. This unique experimental approach allows us to investigate many of the proposed explanations for nonexponential kinetics in nucleic acid dissociation that have, until now, been difficult to isolate.

  15. Gas Hydrate Dissociation in the Ocean

    NASA Astrophysics Data System (ADS)

    Conroy, Devin; Smith, Stefan Llewellyn

    2006-11-01

    Methane gas is known to exist in extremely large quantities below the sea floor in the sediment of the deep and cold oceanic and in permafrost regions. Due to the large hydrostatic pressure and cool temperatures the gas reacts with the surrounding water to form a crystalline substance known as a gas hydrate. The fate of these reserves is very important to climate on earth because methane is a much more efficient greenhouse gas then carbon dioxide. The dissociation process in general can occur by either a decrease in pressure or an increase in temperature. In this study we concentrate on the latter. Once the hydrate dissociates, water and free gas remain above the phase boundary, occupying a larger volume than the original solid, and are be transported through the sediment. We have modeled this physical mechanism using volume averaged equations in a porous medium with a coupled two-phase flow. The movement of the phase boundary, which is proportional to the rate of heat transfer to this interface, is modeled as a Stefan type melting problem. The resultant governing equations are solved numerically, using a front fixing method to fix the phase boundary, to determine the rate of gas flux through the sediment and the dissociation rate.

  16. How thioredoxin dissociates its mixed disulfide.

    PubMed

    Roos, Goedele; Foloppe, Nicolas; Van Laer, Koen; Wyns, Lode; Nilsson, Lennart; Geerlings, Paul; Messens, Joris

    2009-08-01

    The dissociation mechanism of the thioredoxin (Trx) mixed disulfide complexes is unknown and has been debated for more than twenty years. Specifically, opposing arguments for the activation of the nucleophilic cysteine as a thiolate during the dissociation of the complex have been put forward. As a key model, the complex between Trx and its endogenous substrate, arsenate reductase (ArsC), was used. In this structure, a Cys29(Trx)-Cys89(ArsC) intermediate disulfide is formed by the nucleophilic attack of Cys29(Trx) on the exposed Cys82(ArsC)-Cys89(ArsC) in oxidized ArsC. With theoretical reactivity analysis, molecular dynamics simulations, and biochemical complex formation experiments with Cys-mutants, Trx mixed disulfide dissociation was studied. We observed that the conformational changes around the intermediate disulfide bring Cys32(Trx) in contact with Cys29(Trx). Cys32(Trx) is activated for its nucleophilic attack by hydrogen bonds, and Cys32(Trx) is found to be more reactive than Cys82(ArsC). Additionally, Cys32(Trx) directs its nucleophilic attack on the more susceptible Cys29(Trx) and not on Cys89(ArsC). This multidisciplinary approach provides fresh insights into a universal thiol/disulfide exchange reaction mechanism that results in reduced substrate and oxidized Trx. PMID:19675666

  17. Dissociative Disorders Among Chinese Inpatients Diagnosed With Schizophrenia

    PubMed Central

    Yu, Junhan; Ross, Colin A.; Keyes, Benjamin B.; Li, Ying; Dai, Yunfei; Zhang, Tianhong; Wang, Lanlan; Fan, Qing; Xiao, Zeping

    2010-01-01

    The purpose of the study was to assess the prevalence of dissociative disorders in a sample of Chinese psychiatric inpatients. Participants in the study consisted of 569 consecutively admitted inpatients at Shanghai Mental Health Center, China, of whom 84.9% had a clinical diagnosis of schizophrenia based on the Chinese Classification and Diagnostic Criteria for Mental Disorders, Version 3 (CCMD-3). All participants completed a self-report measure of dissociation, the Dissociative Experiences Scale (DES) and none had a prior diagnosis of a dissociative disorder. Ninety-six randomly selected participants were interviewed with a structured interview, the Dissociative Disorders Interview Schedule (DDIS) and a clinical interview. These 96 patients did not differ significantly from the 473 patients who were not interviewed on any demographic measures or on the self-report measure dissociation. A total of 28 (15.3%, after weighting of the data) patients received a clinical diagnosis of a dissociative disorder based on DSM-IV-TR criteria. Dissociative identity disorder was diagnosed in 2 (0.53%, after weighting) patients. Compared to the patients without a dissociative disorder, patients with dissociative disorders were significantly more likely to report childhood abuse (57.1% versus 22.1%), but the two groups did not differ significantly on any demographic measures. Dissociative disorders were readily identified in an inpatient psychiatric population in China. PMID:20603768

  18. Dissociation, PTSD, and substance abuse: an empirical study.

    PubMed

    Najavits, Lisa M; Walsh, Marybeth

    2012-01-01

    Few studies have examined the relationship between posttraumatic stress disorder (PTSD), substance use disorder, and dissociation. We studied 77 women with current PTSD and substance dependence, classified into high- versus low-dissociation groups per the Dissociative Experiences Scale. They were compared on trauma- and substance-related symptoms, cognitions, coping skills, social adjustment, trauma history, psychiatric symptoms, and self-harm/suicidal behaviors. We found the high-dissociation group consistently more impaired than the low-dissociation group. Also, the sample overall evidenced relatively high levels of dissociation, indicating that even in the presence of recent substance use, dissociation remains a major psychological phenomenon. Indeed, the high-dissociation group reported stronger expectation that substances could manage their psychiatric symptoms. The high-dissociation group also had more trauma-related symptoms and childhood histories of emotional abuse and physical neglect. The discussion addresses methodology, the "chemical dissociation" hypothesis, and the need for a more nuanced understanding of how substances are experienced in relation to dissociative phenomena. PMID:22211445

  19. Size-dependent dissociation of carbon monoxide on cobalt nanoparticles.

    PubMed

    Tuxen, Anders; Carenco, Sophie; Chintapalli, Mahati; Chuang, Cheng-Hao; Escudero, Carlos; Pach, Elzbieta; Jiang, Peng; Borondics, Ferenc; Beberwyck, Brandon; Alivisatos, A Paul; Thornton, Geoff; Pong, Way-Faung; Guo, Jinghua; Perez, Ruben; Besenbacher, Flemming; Salmeron, Miquel

    2013-02-13

    In situ soft X-ray absorption spectroscopy (XAS) was employed to study the adsorption and dissociation of carbon monoxide molecules on cobalt nanoparticles with sizes ranging from 4 to 15 nm. The majority of CO molecules adsorb molecularly on the surface of the nanoparticles, but some undergo dissociative adsorption, leading to oxide species on the surface of the nanoparticles. We found that the tendency of CO to undergo dissociation depends critically on the size of the Co nanoparticles. Indeed, CO molecules dissociate much more efficiently on the larger nanoparticles (15 nm) than on the smaller particles (4 nm). We further observed a strong increase in the dissociation rate of adsorbed CO upon exposure to hydrogen, clearly demonstrating that the CO dissociation on cobalt nanoparticles is assisted by hydrogen. Our results suggest that the ability of cobalt nanoparticles to dissociate hydrogen is the main parameter determining the reactivity of cobalt nanoparticles in Fischer-Tropsch synthesis. PMID:23339635

  20. Development, reliability, and validity of a child dissociation scale.

    PubMed

    Putnam, F W; Helmers, K; Trickett, P K

    1993-01-01

    Dissociation is a complex psychophysiological process that ranges along a continuum from minor, normal dissociation to Axis I psychopathology. High levels of dissociation are associated with increased self-destructive behaviors and other symptoms. Although several validated measures of dissociation exist for adults, no measures are available for children. The Child Dissociative Checklist (CDC) was developed to meet this need and is a reliable and valid observer report measure of dissociation in children. The CDC had a 1-year test-retest reliability coefficient of rho = .69 (N = 73, p = .0001) in a sample of normal and sexually abused girls. The CDC had high discriminant validity among four test samples including: normal control girls, sexually abused girls, boys and girls with dissociative disorder NOS and boys and girls with multiple personality disorder. The CDC is intended as a clinical screening instrument and as a research measure. The CDC is not designed to be used as a diagnostic instrument. PMID:8287286

  1. Exploring the relationships between dissociation, victimization, and juvenile sexual offending.

    PubMed

    Leibowitz, George S; Laser, Julie A; Burton, David L

    2011-01-01

    An etiological model of sexually abusive behavior including dissociation could have utility for researchers and treatment providers working with sexually abusive youth with trauma histories. This article explores relationships between dissociation, victimization, and juvenile sexual offending. Self-reported data on dissociation and 5 types of abuse were collected from 2 racially/ethnically diverse groups of sexually abusive and general delinquent male adolescents (n = 502). Bivariate analysis showed significant correlations between all types of child abuse and dissociation with the exception of emotional neglect. Hierarchical logistic regression analysis indicated that dissociation was significant in predicting sexual offender status. Moreover, dissociation, sexual victimization, and physical abuse showed significant effects in predicting membership in the sexual offender group. The results confirm the need for additional research in the areas of assessment and treatment of dissociation among sexually abusive youth. PMID:21240737

  2. Zero-Point Energy Constraint for Unimolecular Dissociation Reactions. Giving Trajectories Multiple Chances To Dissociate Correctly.

    PubMed

    Paul, Amit K; Hase, William L

    2016-01-28

    A zero-point energy (ZPE) constraint model is proposed for classical trajectory simulations of unimolecular decomposition and applied to CH4* → H + CH3 decomposition. With this model trajectories are not allowed to dissociate unless they have ZPE in the CH3 product. If not, they are returned to the CH4* region of phase space and, if necessary, given additional opportunities to dissociate with ZPE. The lifetime for dissociation of an individual trajectory is the time it takes to dissociate with ZPE in CH3, including multiple possible returns to CH4*. With this ZPE constraint the dissociation of CH4* is exponential in time as expected for intrinsic RRKM dynamics and the resulting rate constant is in good agreement with the harmonic quantum value of RRKM theory. In contrast, a model that discards trajectories without ZPE in the reaction products gives a CH4* → H + CH3 rate constant that agrees with the classical and not quantum RRKM value. The rate constant for the purely classical simulation indicates that anharmonicity may be important and the rate constant from the ZPE constrained classical trajectory simulation may not represent the complete anharmonicity of the RRKM quantum dynamics. The ZPE constraint model proposed here is compared with previous models for restricting ZPE flow in intramolecular dynamics, and connecting product and reactant/product quantum energy levels in chemical dynamics simulations. PMID:26738691

  3. Ab initio calculations of dissociative attachment and dissociative recombination of electrons and polyatomic species

    NASA Astrophysics Data System (ADS)

    Haxton, Daniel

    2009-05-01

    Interactions of free electrons with neutral and positively charged molecular species play a role in various physical systems. In interstellar space, reactions such as dissociative recombination determine the balance of various charged and neutral species. In a laboratory equipped with an apparatus like a COLTRIMS device, the dissociative attachment process can be used as a microscope to study polyatomic molecular dynamics. We discuss the theoretical and numerical methods used to calculate dissociative attachment and dissociative recombination of electrons with larger molecules from first principles. Studies using these methods are complimentary to other methods that yield more approximate reaction rates at greatly lesser numerical cost; they may yield precise information about the dissociation dynamics, product distribution, and differential cross section that approximate methods cannot. We discuss calculations performed to date on the target species H2O, NO2, and LiH2^+. We discuss the scaling of our numerical methods with the number of atoms, and the prospects of applying them to tetra-atomics.

  4. Dissociative depression among women with fibromyalgia or rheumatoid arthritis.

    PubMed

    Kilic, Ozge; Sar, Vedat; Taycan, Okan; Aksoy-Poyraz, Cana; Erol, Turgut C; Tecer, Ozlem; Emul, Murat H; Ozmen, Mine

    2014-01-01

    The aim of this study was to inquire about the possible relations of childhood trauma, anger, and dissociation to depression among women with fibromyalgia or rheumatoid arthritis. Fifty female patients diagnosed as having fibromyalgia (n = 30) or rheumatoid arthritis (n = 20) participated in the study. The Childhood Trauma Questionnaire, Somatoform Dissociation Questionnaire (SDQ), Dissociation Questionnaire (DIS-Q), Beck Depression Inventory (BDI), Spielberger State-Trait Anger Expression Inventory, and Dissociative Disorders Interview Schedule were administered to all participants. Women with a lifetime diagnosis of depressive disorder had higher scores for somatoform and psychoform dissociation than the nondepressive patients. However, childhood trauma scores did not differ between the 2 groups. In regression analysis, current severity of depression (BDI) was predicted by psychoform dissociation (DIS-Q) and lower education, and lifetime diagnosis of major depression was predicted by somatoform dissociation (SDQ). Whereas childhood emotional neglect predicted somatoform dissociation, psychoform dissociation was predicted by childhood sexual abuse. Mental processing of anger seems to be 1 of the dimensions of psychodynamics in trauma-related depressive conditions. In the context of the perceived threat of loss of control due to expressed anger and mental disintegration, somatoform dissociation seems to contribute to overmodulation of emotions in dissociative depression. Among patients suffering from physical illness with possible psychosomatic dimensions, assessment of somatoform dissociation in addition to psychoform dissociation may be helpful to understand diverse psychopathological trajectories emerging in the aftermath of childhood adversities. The recently proposed category of "dissociative depression" (Sar, 2011) seems to be a promising concept for future research on psychosomatic aspects of traumatic stress. PMID:24228798

  5. Mechanisms and energetics of hydride dissociation reactions on surfaces of plasma-deposited silicon thin films

    NASA Astrophysics Data System (ADS)

    Singh, Tejinder; Valipa, Mayur S.; Mountziaris, T. J.; Maroudas, Dimitrios

    2007-11-01

    We report results from a detailed analysis of the fundamental silicon hydride dissociation processes on silicon surfaces and discuss their implications for the surface chemical composition of plasma-deposited hydrogenated amorphous silicon (a-Si:H) thin films. The analysis is based on a synergistic combination of first-principles density functional theory (DFT) calculations of hydride dissociation on the hydrogen-terminated Si(001)-(2×1) surface and molecular-dynamics (MD) simulations of adsorbed SiH3 radical precursor dissociation on surfaces of MD-grown a-Si :H films. Our DFT calculations reveal that, in the presence of fivefold coordinated surface Si atoms, surface trihydride species dissociate sequentially to form surface dihydrides and surface monohydrides via thermally activated pathways with reaction barriers of 0.40-0.55eV. The presence of dangling bonds (DBs) results in lowering the activation barrier for hydride dissociation to 0.15-0.20eV, but such DB-mediated reactions are infrequent. Our MD simulations on a-Si :H film growth surfaces indicate that surface hydride dissociation reactions are predominantly mediated by fivefold coordinated surface Si atoms, with resulting activation barriers of 0.35-0.50eV. The results are consistent with experimental measurements of a-Si :H film surface composition using in situ attenuated total reflection Fourier transform infrared spectroscopy, which indicate that the a-Si :H surface is predominantly covered with the higher hydrides at low temperatures, while the surface monohydride, SiH(s ), becomes increasingly more dominant as the temperature is increased.

  6. Dissociative symptoms and dissociative disorders comorbidity in obsessive compulsive disorder: Symptom screening, diagnostic tools and reflections on treatment.

    PubMed

    Belli, Hasan

    2014-08-16

    Borderline personality disorder, conversion disorder and obsessive compulsive disorder frequently have dissociative symptoms. The literature has demonstrated that the level of dissociation might be correlated with the severity of obsessive compulsive disorder (OCD) and that those not responding to treatment had high dissociative symptoms. The structured clinical interview for DSM-IV dissociative disorders, dissociation questionnaire, somatoform dissociation questionnaire and dissociative experiences scale can be used for screening dissociative symptoms and detecting dissociative disorders in patients with OCD. However, a history of neglect and abuse during childhood is linked to a risk factor in the pathogenesis of dissociative psychopathology in adults. The childhood trauma questionnaire-53 and childhood trauma questionnaire-40 can be used for this purpose. Clinicians should not fail to notice the hidden dissociative symptoms and childhood traumatic experiences in OCD cases with severe symptoms that are resistant to treatment. Symptom screening and diagnostic tools used for this purpose should be known. Knowing how to treat these pathologies in patients who are diagnosed with OCD can be crucial. PMID:25133142

  7. Dissociation, PTSD, and Substance Abuse: An Empirical Study

    PubMed Central

    Najavits, Lisa; Walsh, Marybeth

    2012-01-01

    Few studies have examined the relationship between posttraumatic stress disorder (PTSD), substance use disorder (SUD) and dissociation. We studied 77 women with current PTSD and substance dependence, classified into high- versus low-dissociation on the Dissociative Experiences Scale. They were compared on trauma- and substance-related symptoms, cognitions, coping skills, social adjustment, trauma history, psychiatric symptoms, and self-harm/suicidal behaviors. We found the high-dissociation group consistently more impaired than the low-dissociation group. Also, the sample overall evidenced relatively high levels of dissociation, indicating that even in the presence of recent substance use, dissociation remains a major psychological phenomenon. Indeed, the high-dissociation group reported stronger expectation that substances could manage their psychiatric symptoms. The high-dissociation group also had more trauma-related symptoms and childhood histories of emotional abuse and physical neglect. Discussion addresses methodology, the “chemical dissociation” hypothesis, and the need for more nuanced understanding of how substances are experienced in relation to dissociative phenomena. PMID:22211445

  8. The role of water in gas hydrate dissociation

    USGS Publications Warehouse

    Circone, S.; Stern, L.A.; Kirby, S.H.

    2004-01-01

    When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

  9. Different urea stoichiometries between the dissociation and denaturation of tobacco mosaic virus as probed by hydrostatic pressure.

    PubMed

    Santos, Jose L R; Aparicio, Ricardo; Joekes, Inés; Silva, Jerson L; Bispo, Jose A C; Bonafe, Carlos F S

    2008-05-01

    Viruses are very efficient self-assembly structures, but little is understood about the thermodynamics governing their directed assembly. At higher levels of pressure or when pressure is combined with urea, denaturation occurs. For a better understanding of such processes, we investigated the apparent thermodynamic parameters of dissociation and denaturation by assuming a steady-state condition. These processes can be measured considering the decrease of light scattering of a viral solution due to the dissociation process, and the red shift of the fluorescence emission spectra, that occurs with the denaturation process. We determined the apparent urea stoichiometry considering the equilibrium reaction of TMV dissociation and subunit denaturation, which furnished, respectively, 1.53 and 11.1 mol of urea/mol of TMV subunit. The denaturation and dissociation conditions were arrived in a near reversible pathway, allowing the determination of thermodynamic parameters. Gel filtration HPLC, electron microscopy and circular dichroism confirmed the dissociation and denaturation processes. Based on spectroscopic results from earlier papers, the calculation of the apparent urea stoichiometry of dissociation and denaturation of several other viruses resulted in similar values, suggesting a similar virus-urea interaction among these systems. PMID:18367310

  10. A preliminary study of cortisol and norepinephrine reactivity to psychosocial stress in borderline personality disorder with high and low dissociation.

    PubMed

    Simeon, Daphne; Knutelska, Margaret; Smith, Lisa; Baker, Bryann R; Hollander, Eric

    2007-01-15

    The goal of the current study was to investigate subjective and neurohormonal reactivity to acute psychosocial stress in borderline personality disorder (BPD) as a function of dissociative symptoms. Five BPD subjects with high dissociation, 8 BPD subjects with low dissociation, and 11 healthy control subjects were compared in basal urinary cortisol and norepinephrine, as well as in plasma cortisol and norepinephrine reactivity to the Trier Social Stress Test (TSST). Subjective stress rating and emotional response to the TSST were also measured. The three groups differed significantly in cortisol stress reactivity, with the high-dissociation BPD group demonstrating the most robust response. The three groups did not significantly differ in norepinephrine stress reactivity. In the combined BPD sample, dissociation severity tended to be inversely correlated with basal urinary norepinephrine, was positively correlated with norepinephrine stress reactivity. Childhood trauma was inversely correlated with basal urinary cortisol. In conclusion, despite its small sample size this pilot study suggests that dissociative symptomatology may be a marker of heightened biological vulnerability to stress in BPD, and merits further study. PMID:17169436

  11. Kinetics of calcium dissociation from its high-affinity transport sites on sarcoplasmic reticulum ATPase.

    PubMed

    Orlowski, S; Champeil, P

    1991-01-15

    We investigated the kinetics of calcium dissociation from its high-affinity transport sites on sarcoplasmic reticulum Ca2(+)-ATPase by combining fast filtration with stopped-flow fluorescence measurements. At pH 6 and 20 degrees C, in the absence of potassium and in the presence of 20 mM MgCl2, isotopic exchange of bound calcium exhibited biphasic kinetics, with two phases of equal amplitude, regardless of the initial extent of binding site saturation. The rapidly exchangeable site, whose occupancy by calcium controlled the rate constant of the slow phase, had an apparent affinity for calcium of about 3-6 microM. A similar high affinity was also deduced from measurements of the calcium dependence of the rate constant for ATPase fluorescence changes. This affinity was higher than the overall affinity for calcium deduced from the equilibrium binding measurements (dissociation constant of 15-20 microM); this was consistent with the occurrence of cooperativity (Hill coefficient of 1.6-1.8). The drop in intrinsic fluorescence observed upon chelation of calcium was always slightly faster than the dissociation of calcium itself, although the rates for both this drop in fluorescence and calcium dissociation varied slightly from one preparation to the other. This fluorescence drop was therefore mainly due to dissociation of the bound ions, not to slow transconformation of the ATPase. Dissociation of the two bound calcium ions in a medium containing EGTA exhibited monophasic kinetics in the presence of a calcium ionophore, with a rate constant about half that of the fast phase of isotopic exchange. This particular pattern was observed over a wide range of experimental conditions, including the presence of KCl, dimethyl sulfoxide, 4-nonylphenol, or a nucleotide analogue, at pH 6 or 7, and at various temperatures. The kinetics of calcium dissociation under the above various conditions were not correlated with the ATPase affinity for calcium deduced from equilibrium

  12. Imagination and dissociation in hypnotic responding.

    PubMed

    Bowers, K S

    1992-10-01

    A neodissociative model of mind is better equipped than a social-psychological model to deal with the complexities of hypnosis, and of human behavior generally. It recognizes, as Coe's (1992) model does not, that behavior can be more automatically activated than strategically enacted. In particular, Coe's emphasis on human behavior as purposeful and goal directed does not distinguish between goal-directed behavior that serves a purpose, and goal-directed behavior that is performed on purpose. It is this distinction that permits goal-directed behavior to be dissociated from a person's conscious plans and intentions. In addition to offering a critique of Coe's "limited process" view of hypnosis, 4 main points are made in the interest of developing a slightly modified, neodissociation view of hypnosis. First, it is argued that goal-directed fantasies are more limited in their ability to mediate hypnotic responding than is commonly appreciated; as well, they do not seem to account for the nonvolitional quality of hypnotic responding. Second, it is argued that hypnotic ability is not unidimensional, with compliance and social influence more apt to account for the low than for the high hypnotizable's responsiveness to suggestion. Third, compared to low hypnotizables, the hypnotic responsiveness of high hypnotizables seems more likely to result from dissociated control. In other words, for high hypnotizables, hypnotic suggestions may often directly activate subsystems of cognitive control. Consequently, the need for executive initiative and effort to produce hypnotically suggested behavior is minimized, and such responses are therefore experienced as nonvolitional. Fourth and finally, while goal-directed fantasies typically accompany hypnotically suggested responses, they are in many cases more a marker of dissociated control than a mediator of suggested effects. PMID:1468834

  13. On the dissociation energy of Mg2

    NASA Technical Reports Server (NTRS)

    Partridge, Harry; Bauschlicher, Charles W., Jr.; Pettersson, Lars G. M.; Mclean, A. D.; Liu, Bowen

    1990-01-01

    The bonding in the X 1Sigma(+)g state of Mg2 is investigated using near-complete valence one-particle Slater and Gaussian basis sets containing up to h functions. It is shown that the four-electron complete CI limit can be approached using a sequence of either second-order CI (SOCI) or interacting correlated fragment (ICF) calculations. At the valence level, the best estimate of the dissociation energy D(e) was 464/cm. This is a lower limit and is probably within 5/cm of the complete basis value.

  14. Spin–orbit interaction mediated molecular dissociation

    SciTech Connect

    Kokkonen, E. Jänkälä, K.; Kettunen, J. A.; Heinäsmäki, S.; Karpenko, A.; Huttula, M.; Löytynoja, T.

    2014-05-14

    The effect of the spin–orbit interaction to photofragmentation is investigated in the mercury(II) bromide (HgBr{sub 2}) molecule. Changes in the fragmentation between the two spin–orbit components of Hg 5d photoionization, as well as within the molecular-field-splitted levels of these components are observed. Dissociation subsequent to photoionization is studied with synchrotron radiation and photoelectron-photoion coincidence spectroscopy. The experimental results are accompanied by relativistic ab initio analysis of the photoelectron spectrum.

  15. Dissociative Ionization of Aromatic and Heterocyclic Molecules

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.

    2003-01-01

    Space radiation poses a major health hazard to humans in space flight. The high-energy charged particles in space radiation ranging from protons to high atomic number, high-energy (HZE) particles, and the secondary species they produce, attack DNA, cells, and tissues. Of the potential hazards, long-term health effects such as carcinogenesis are likely linked to the DNA lesions caused by secondary electrons in the 1 - 30 eV range. Dissociative ionization (DI) is one of the electron collision processes that can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. To understand this process, we have developed a theoretical model for DI. Our model makes use of the fact that electron motion is much faster than nuclear motion and assumes DI proceeds through a two-step process. The first step is electron-impact ionization resulting in a particular state of the molecular ion in the geometry of the neutral molecule. In the second step the ion undergoes unimolecular dissociation. Thus the DI cross section sigma(sup DI)(sub a) for channel a is given by sigma(sup DI)(sub a) = sigma(sup I)(sub a) P(sub D) with sigma(sup I)(sub a) the ionization cross section of channel a and P(sub D) the dissociation probability. This model has been applied to study the DI of H2O, NH3, and CH4, with results in good agreement with experiment. The ionization cross section sigma(sup I)(sub a) was calculated using the improved binary encounter-dipole model and the unimolecular dissociation probability P(sub D) obtained by following the minimum energy path determined by the gradients and Hessians of the electronic energy with respect to the nuclear coordinates of the ion. This model is used to study the DI from the low-lying channels of benzene and pyridine to understand the different product formation in aromatic and heterocyclic molecules. DI study of the DNA base thymine is underway. Solvent effects will also be discussed.

  16. Occipitocervical dissociation-incidence, evaluation, and treatment.

    PubMed

    Kasliwal, Manish K; Fontes, Ricardo B; Traynelis, Vincent C

    2016-09-01

    Traumatic occipitocervical dissociation (OCD) results from ligamentous injury to the craniocervical junction and is associated with a high rate of mortality and significant neurologic morbidity. The diagnosis is frequently missed on initial lateral cervical spinal radiographs mainly due to inadequate visualization of radiological landmarks and low degree of suspicion. Widespread availability of multidetector computed tomography (MDCT) of the spine and development of better diagnostic radiological criteria has allowed timely diagnosis and good clinical outcome following posterior occipitocervical fusion and instrumentation for a pathology that was once considered uniformly fatal. The present paper reviews the clinical features, diagnosis, and management of OCD in light of most recent literature. PMID:27255101

  17. Towards an accurate dissociative potential for water

    NASA Astrophysics Data System (ADS)

    Akin-Ojo, Omololu

    2014-03-01

    Most models of water describe the molecule as rigid, i.e., with fixed bond angles and bond lengths, or as flexible in which the bond angles and bond lengths vary but the chemical bonds cannot be broken. In this work we present our progress in the development of a water model which allows for the breaking and formation of chemical bonds. The force field was obtained by fitting ab initio (not DFT) energies, forces, and molecular properties. The ability of the model to predict properties of water at ambient and extreme conditions will be presented. We will also report on the modeling of small clusters of water using the dissociative force field.

  18. Dissociation in individuals denying trauma exposure: findings from two samples.

    PubMed

    Briere, John; Runtz, Marsha

    2015-06-01

    A number of studies suggest that dissociation is reliably related to trauma exposure, and that inadequate regulation of posttraumatic distress may be a significant factor. We examined whether affect dysregulation predicts dissociation in those denying any lifetime exposure to trauma. These relationships were evaluated in a general population sample and a second sample of nontraumatized university students. In the first study, multivariate analyses indicated that, along with gender, affect dysregulation was a relatively strong predictor, accounting for 27% of the variance in dissociation. In the replication study, dissociation was associated with affect dysregulation, but not gender. Affect dysregulation seems to predict dissociative symptomatology in nontraumatized individuals. It is hypothesized that emotional distress, whether from trauma or other etiologies, motivates dissociation to the extent that it challenges the individual's compromised capacity for affect regulation. Treatment implications may include the potential helpfulness of interventions that increase emotion regulation skills. PMID:25974057

  19. Dissociative experience and cultural neuroscience: narrative, metaphor and mechanism.

    PubMed

    Seligman, Rebecca; Kirmayer, Laurence J

    2008-03-01

    Approaches to trance and possession in anthropology have tended to use outmoded models drawn from psychodynamic theory or treated such dissociative phenomena as purely discursive processes of attributing action and experience to agencies other than the self. Within psychology and psychiatry, understanding of dissociative disorders has been hindered by polemical "either/or" arguments: either dissociative disorders are real, spontaneous alterations in brain states that reflect basic neurobiological phenomena, or they are imaginary, socially constructed role performances dictated by interpersonal expectations, power dynamics and cultural scripts. In this paper, we outline an approach to dissociative phenomena, including trance, possession and spiritual and healing practices, that integrates the neuropsychological notions of underlying mechanism with sociocultural processes of the narrative construction and social presentation of the self. This integrative model, grounded in a cultural neuroscience, can advance ethnographic studies of dissociation and inform clinical approaches to dissociation through careful consideration of the impact of social context. PMID:18213511

  20. The relationship between catatonia and dissociation: A preliminary investigation.

    PubMed

    Ross, Colin A; Browning, Elena

    2016-01-01

    Unlike the relationship between dissociation and Schneiderian first-rank symptoms, the relationship between dissociation and catatonia has not been investigated empirically. In order to gather some initial data about catatonia, dissociation, and childhood adverse experiences, we administered the Bush-Francis Catatonia Scale (BFCS), the Dissociative Experiences Scale (DES), the Adverse Childhood Experiences Questionnaire, and the Dissociative Disorders Interview Schedule to 100 inpatients in a hospital trauma program. The average DES score was 44.1 (SD = 22.4), and 86 participants were in the DES-Taxon. The average score on the BFCS was 7.7 (SD = 10.3); 81 participants scored 2 or higher, and 67 scored 5 or higher. The results showed that, in this sample, catatonic symptoms are frequent and related to adverse childhood experiences but seem to be a separate symptom category from both dissociation and psychosis. PMID:26751346

  1. Strain-induced water dissociation on supported ultrathin oxide films

    NASA Astrophysics Data System (ADS)

    Song, Zhenjun; Fan, Jing; Xu, Hu

    2016-03-01

    Controlling the dissociation of single water molecule on an insulating surface plays a crucial role in many catalytic reactions. In this work, we have identified the enhanced chemical reactivity of ultrathin MgO(100) films deposited on Mo(100) substrate that causes water dissociation. We reveal that the ability to split water on insulating surface closely depends on the lattice mismatch between ultrathin films and the underlying substrate, and substrate-induced in-plane tensile strain dramatically results in water dissociation on MgO(100). Three dissociative adsorption configurations of water with lower energy are predicted, and the structural transition going from molecular form to dissociative form is almost barrierless. Our results provide an effective avenue to achieve water dissociation at the single-molecule level and shed light on how to tune the chemical reactions of insulating surfaces by choosing the suitable substrates.

  2. Dissociative detachment relates to psychotic symptoms and personality decompensation.

    PubMed

    Allen, J G; Coyne, L; Console, D A

    1997-01-01

    Previous studies have addressed the prominence of psychotic symptoms in conjunction with multiple personality disorder (now dissociative identity disorder). The present study examines the relation between psychotic symptoms and a more pervasive form of dissociative disturbance, namely dissociative detachment. Two hundred sixty-six women in inpatient treatment for severe trauma-related disorders completed the Dissociative Experiences Scale (DES), and 102 of these patients also completed the Millon Clinical Multiaxial Inventory (MCMI-III). A factor analysis of the DES yielded two dimensions of dissociative detachment: detachment from one's own actions and detachment from the self and the environment. Each of these DES dimensions relates strongly to the thought disorder and schizotypal personality disorder scales of the MCMI-III. We propose that severe dissociative detachment, by virtue of loosening the moorings in inner and outer reality, is conducive to psychotic symptoms and personality decompensation. PMID:9406738

  3. Being in rhythm: dissociative attunement in therapeutic process.

    PubMed

    Hopenwasser, Karen

    2008-01-01

    Dissociative attunement is a profound rhythmic encounter in therapeutic treatment. Attunement is a synchronized awareness of implicit knowing that is nonlinear and bidirectional. Empathically attuned clinicians are like microtonal tuning forks. They resonate with a variety of emotional pitches and will resonate with nuanced shifting of emotional tone. This resonance is the basis of dissociative attunement. Concepts such as empathic attunement, affect attunement, "the unthought known," "implicit relational knowing," and "a two-person unconscious" help us to understand unique aspects of projective identification, transference, and countertransference within the dissociative frame. However, "dissociative" attunements are systemically self-emergent moments in which multiple self-states are shared by means other than projection. Using clinical vignettes, I demonstrate how dissociative attunement can paradoxically appear to be misattunement. By synthesizing scientific and theoretical concepts applied to these clinical moments, we can understand dissociative attunement as a therapeutic tool as well as a pathway to vicarious traumatization. PMID:19042783

  4. Strain-induced water dissociation on supported ultrathin oxide films

    PubMed Central

    Song, Zhenjun; Fan, Jing; Xu, Hu

    2016-01-01

    Controlling the dissociation of single water molecule on an insulating surface plays a crucial role in many catalytic reactions. In this work, we have identified the enhanced chemical reactivity of ultrathin MgO(100) films deposited on Mo(100) substrate that causes water dissociation. We reveal that the ability to split water on insulating surface closely depends on the lattice mismatch between ultrathin films and the underlying substrate, and substrate-induced in-plane tensile strain dramatically results in water dissociation on MgO(100). Three dissociative adsorption configurations of water with lower energy are predicted, and the structural transition going from molecular form to dissociative form is almost barrierless. Our results provide an effective avenue to achieve water dissociation at the single-molecule level and shed light on how to tune the chemical reactions of insulating surfaces by choosing the suitable substrates. PMID:26953105

  5. Visible/Infrared Dissociation of NO3: Roaming in the Dark or Roaming on the Ground?

    PubMed

    Fernando, Ravin; Dey, Arghya; Broderick, Bernadette M; Fu, Bina; Homayoon, Zahra; Bowman, Joel M; Suits, Arthur G

    2015-07-16

    We present a DC slice imaging study of roaming dynamics in the photodissociation of the nitrate radical, NO3, contrasting pure visible excitation with a combination of visible and CO2 laser excitation at 10.6 μm. Images of specific rotational levels of NO are seen to reflect dissociation on the ground and first excited electronic states, as reported in previous work. The branching is obtained for specific rotational levels by comparison to quasiclassical trajectory calculations of the dynamics on these two surfaces. The results for the visible dissociation are found to be very similar to the combination of visible and infrared, raising questions about the nature of the coupling of these surfaces, the extent to which roaming takes place on both, and how the final product branching is determined. PMID:25407947

  6. Ictal symptoms of anxiety, avoidance behaviour, and dissociation in patients with dissociative seizures

    PubMed Central

    Goldstein, L H; Mellers, J D C

    2006-01-01

    Objective To examine anxiety related seizure symptoms and avoidance behaviour in adults with dissociative (psychogenic non‐epileptic) seizures (DS) in comparison with a group suffering from partial epilepsy. Methods 25 DS and 19 epilepsy patients completed an attack symptom measure, the hospital anxiety and depression scale, the dissociative experiences scale, and the fear questionnaire. Results DS patients reported the presence of significantly greater numbers of somatic symptoms of anxiety during their attacks than the epilepsy group, despite not reporting subjectively higher levels of anxiety. The DS patients also reported higher levels of agoraphobic‐type avoidance behaviour than the epilepsy group. Measures of dissociation were higher in the DS group, who also reported greater symptoms of depression. Conclusions The findings support a model whereby DS occur as a paroxysmal, dissociative response to heightened arousal in the absence of raised general anxiety levels. The model has practical implications for clinical assessment and treatment: in clinical practice, inquiry about these symptoms may help in the diagnosis of DS; with respect to treatment, the anxiety related symptoms and avoidance behaviour prevalent in DS are a potential focus for a cognitive behavioural approach analogous to that used in the treatment of other anxiety disorders. PMID:16614021

  7. Simulation studies of the dissociation of H 2 on stepped surfaces

    NASA Astrophysics Data System (ADS)

    Kaukonen, H.-P.; Nieminen, R. M.

    1991-05-01

    We have simulated the dissociation reaction of H 2 on stepped ideal honeycomb, square and hexagonal surfaces with a simple kinetic model based on the idea proposed by Poelsema and Comsa [Scattering of Thermal Energy Atoms from Disordered Surfaces, Springer Tracts in Modern Physics 115 (Springer, Berlin, 1989)] that dissociation on a stepped Pt(111) surface occurs exclusively on step sites. The observed sticking coefficient sH 2 of H 2 consists of two competing channels: (1) physisorbed molecules incident on terrace sites diffusing to the step, and (2) direct dissociation of molecules incident on or near a step site. The results support this picture qualitatively and indicate that the behaviour of the system can be separated depending on surface temperature into three domains in each of which a different mechanism dominates. (1) T < T1: a geometric effect, i.e. the cluster size distribution of vacant adsorption sites on the surface, (2) T1 < T < T2: a geometric effect combined with nearest neighbour interactions due to ad atoms, and (3) T > T2: direct adsorption near a step site. Of the three surfaces structures studied the honeycomb structure corresponds most closely to the observed H 2 dissociation.

  8. The molecular dynamics of adsorption and dissociation of O{sub 2} on Pt(553)

    SciTech Connect

    Jacobse, Leon Dunnen, Angela den; Juurlink, Ludo B. F.

    2015-07-07

    Molecular adsorption and dissociation of O{sub 2} on the stepped Pt(553) surface have been investigated using supersonic molecular beam techniques and temperature programmed desorption. The initial and coverage-dependent sticking probability was determined with the King and Wells technique for various combinations of incident kinetic energy, surface temperature, incident angle, and surface coverage. A comparison with similar data for Pt(533) and Pt(110)(1 × 2) shows quantitatively the same high step-induced sticking at low incident energies compared to Pt(111). The enhancement is therefore insensitive to the exact arrangement of atoms forming surface corrugation. We consider energy transfer and electronic effects to explain the enhanced sticking. On the other hand, dissociation dynamics at higher incident kinetic energies are strongly dependent on step type. The Pt(553) and Pt(533) surfaces are more reactive than Pt(111), but the (100) step shows higher sticking than the (110) step. We relate this difference to a variation in the effective lowering of the barrier to dissociation from molecularly adsorbed states into atomic states. Our findings are in line with results from experimental desorption studies and theoretical studies of atomic binding energies. We discuss the influence of the different step types on sticking and dissociation dynamics with a one-dimensional potential energy surface.

  9. Grammatical category dissociation in multilingual aphasia.

    PubMed

    Faroqi-Shah, Yasmeen; Waked, Arifi N

    2010-03-01

    Word retrieval deficits for specific grammatical categories, such as verbs versus nouns, occur as a consequence of brain damage. Such deficits are informative about the nature of lexical organization in the human brain. This study examined retrieval of grammatical categories across three languages in a trilingual person with aphasia who spoke Arabic, French, and English. In order to delineate the nature of word production difficulty, comprehension was tested, and a variety of concomitant lexical-semantic variables were analysed. The patient demonstrated a consistent noun-verb dissociation in picture naming and narrative speech, with severely impaired production of verbs across all three languages. The cross-linguistically similar noun-verb dissociation, coupled with little evidence of semantic impairment, suggests that (a) the patient has a true "nonsemantic" grammatical category specific deficit, and (b) lexical organization in multilingual speakers shares grammatical class information between languages. The findings of this study contribute to our understanding of the architecture of lexical organization in bilinguals. PMID:20830631

  10. Multigenerational Dissociation: A Framework for Building Narrative.

    PubMed

    McCollum, Sally E

    2015-01-01

    This paper presents the concept of Multigenerational Dissociation (MGD), a behavior pattern that occurs in families in which violence and abuse are re-enacted from one generation to the next, accompanied by denial that the trauma occurred, or if it did, that it was destructive. While revictimization, reenactment, and the intergenerational transmission of trauma are discussed extensively in the literature, MGD helps to view them within a broad historical framework. This is useful for conceptualizing cases therapeutically, and it can also contribute to research on dissociation and recovered memories of trauma and abuse by demonstrating the value of narrative clinical data. Case material is used to illustrate how MGD occurs in people's lives and affects their memories, demonstrating how it becomes a frame within which to convey the dynamics of how traumatic experiences are remembered. This also demonstrates that when clinicians contribute their own narrative data to research on traumatic memory, the science is more accurate, relevant, and comprehensible to clinical and nonclinical researchers. PMID:26158318

  11. Autobiographical memory specificity in dissociative identity disorder.

    PubMed

    Huntjens, Rafaële J C; Wessel, Ineke; Hermans, Dirk; van Minnen, Agnes

    2014-05-01

    A lack of adequate access to autobiographical knowledge has been related to psychopathology. More specifically, patients suffering from depression or a history of trauma have been found to be characterized by overgeneral memory, in other words, they show a relative difficulty in retrieving a specific event from memory located in time and place. Previous studies of overgeneral memory have not included patients with dissociative disorders. These patients are interesting to consider, as they are hypothesized to have the ability to selectively compartmentalize information linked to negative emotions. This study examined avoidance and overgeneral memory in patients with dissociative identity disorder (DID; n = 12). The patients completed the autobiographical memory test (AMT). Their performance was compared with control groups of posttraumatic stress disorder (PTSD) patients (n = 26), healthy controls (n = 29), and DID simulators (n = 26). Specifically, we compared the performance of separate identity states in DID hypothesized to diverge in the use of avoidance as a coping strategy to deal with negative affect. No significant differences in memory specificity were found between the separate identities in DID. Irrespective of identity state, DID patients were characterized by a lack of memory specificity, which was similar to the lack of memory specificity found in PTSD patients. The converging results for DID and PTSD patients add empirical evidence for the role of overgeneral memory involved in the maintenance of posttraumatic psychopathology. PMID:24886016

  12. Dissociation of silica at high pressure

    NASA Astrophysics Data System (ADS)

    Hicks, Damien; Boehly, Tom

    2005-07-01

    Measurements of the temperature and optical reflectivity of quartz and fused silica under shock loading from 100 to 1000 GPa have revealed evidence for dissociation of silica between ˜150 and 400 GPa. Using attenuating laser-driven shock waves a continuous record of the temperature and reflectivity dependence on pressure has been obtained in both materials allowing the specific heat capacity and electronic conductivity to be deduced. Results show that between 150 and 400 GPa the specific heat rises significantly above that expected from the Dulong-Petit law, indicating the presence of a latent energy. Coincident with this anomalous specific heat is a rapid rise in electronic conductivity. Both these observables suggest that dissociation is occurring in the dense fluid. In addition temperature measurements near 5000 K detect a discontinuity at the melt transition, as measured earlier on gas gun experiments. This work was performed under the auspices of the US DOE by LLNL under Contract No. W-7405-ENG-48 and by the University of Rochester under Cooperative Agreement No. DE-FC03-92SF19460.

  13. Dissociable behavioural outcomes of visual statistical learning

    PubMed Central

    Turk-Browne, Nicholas B.; Seitz, Aaron R.

    2016-01-01

    Statistical learning refers to the extraction of probabilistic relationships between stimuli and is increasingly used as a method to understand learning processes. However, numerous cognitive processes are sensitive to the statistical relationships between stimuli and any one measure of learning may conflate these processes; to date little research has focused on differentiating these processes. To understand how multiple processes underlie statistical learning, here we compared, within the same study, operational measures of learning from different tasks that may be differentially sensitive to these processes. In Experiment 1, participants were visually exposed to temporal regularities embedded in a stream of shapes. Their task was to periodically detect whether a shape, whose contrast was staircased to a threshold level, was present or absent. Afterwards, they completed a search task, where statistically predictable shapes were found more quickly. We used the search task to label shape pairs as “learned” or “non-learned”, and then used these labels to analyse the detection task. We found a dissociation between learning on the search task and the detection task where only non-learned pairs showed learning effects in the detection task. This finding was replicated in further experiments with recognition memory (Experiment 2) and associative learning tasks (Experiment 3). Taken together, these findings are consistent with the view that statistical learning may comprise a family of processes that can produce dissociable effects on different aspects of behaviour.

  14. Dissociation of methane under high pressure.

    PubMed

    Gao, Guoying; Oganov, Artem R; Ma, Yanming; Wang, Hui; Li, Peifang; Li, Yinwei; Iitaka, Toshiaki; Zou, Guangtian

    2010-10-14

    Methane is an extremely important energy source with a great abundance in nature and plays a significant role in planetary physics, being one of the major constituents of giant planets Uranus and Neptune. The stable crystal forms of methane under extreme conditions are of great fundamental interest. Using the ab initio evolutionary algorithm for crystal structure prediction, we found three novel insulating molecular structures with P2(1)2(1)2(1), Pnma, and Cmcm space groups. Remarkably, under high pressure, methane becomes unstable and dissociates into ethane (C(2)H(6)) at 95 GPa, butane (C(4)H(10)) at 158 GPa, and further, carbon (diamond) and hydrogen above 287 GPa at zero temperature. We have computed the pressure-temperature phase diagram, which sheds light into the seemingly conflicting observations of the unusually low formation pressure of diamond at high temperature and the failure of experimental observation of dissociation at room temperature. Our results support the idea of diamond formation in the interiors of giant planets such as Neptune. PMID:20950018

  15. Dissociative recombination of molecular ions with electrons

    NASA Technical Reports Server (NTRS)

    Johnsen, Rainer

    1990-01-01

    An overview is presented for the present state of the art of laboratory measurements of the dissociative recombination of molecular ions with electrons. Most work has focussed on obtaining rates and their temperature dependence, as these are of primary interest for model calculations of ionospheres. A comparison of data obtained using the microwave afterglow method, the flowing afterglow technique, and the merged beam technique shows that generally the agreement is quite good, but there are some serious discrepancies, especially in the case of H(3+) recombination, that need to be resolved. Results of some earlier experimental work need to be reexamined in the light of more recent developments. Such cases are pointed out and a compilation of rate coefficients that have withstood scrutiny is presented. Recent advances in experimental methods, such as the use of laser-in-duced fluorescence, make it possible to identify some neutral products of dissociative recombination. What has been done so far and what results one might expect from future work are briefly reviewed.

  16. Dissociative excitation study of iron pentacarbonyl molecule

    NASA Astrophysics Data System (ADS)

    Ribar, Anita; Danko, Marián; Országh, Juraj; Ferreira da Silva, Filipe; Utke, Ivo; Matejčík, Štefan

    2015-04-01

    The processes of dissociative excitation (DE) and dissociative ionisation with excitation (DIE) of iron pentacarbonyl, Fe(CO)5, have been studied using a crossed electron-molecule beam experimental apparatus (Electron Induced Fluorescence Apparatus, EIFA). Using EIFA we were able to record the emission spectrum of the molecule in the UV-VIS range, as well as the photon efficiency curves initiated by electron impact. The emission spectrum of Fe(CO)5 initiated by impact of 50 eV electrons was recorded in the spectral range between 200 nm and 470 nm. It shows a high density of emission lines and bands (mainly iron lines and carbonyl bands). Additionally, we have measured photon efficiency curves (PECs) as a function of the electron impact energy for several lines and bands. On the basis of the PECs we have discussed the reaction mechanism and the energetics of the reactions associated with the DE and DIE processes. Contribution to the Topical Issue "Elementary Processes with Atoms and Molecules in Isolated and Aggregated States", edited by Friedrich Aumayr, Bratislav Marinkovic, Štefan Matejčík, John Tanis and Kurt H. Becker.

  17. Electron Impact Ionization and Dissociative Ionization of C2H2

    NASA Technical Reports Server (NTRS)

    Srivastava, S. K.

    1995-01-01

    By utilizing a crossed electron beam collision geometry, a combination of time-of-flight (TOF) and quadrupole mass spectrometers, and the relative flow technique1 normalized values of cross sections and appearance energies (AP) were obtained for the formation of singly and multiply ionized species resulting from the ionization and dissociation of C2H2. Details ont he apparatus and technique have been published previously.2,3.

  18. Childhood maltreatment and intimate partner violence in dissociative disorder patients

    PubMed Central

    Webermann, Aliya R.; Brand, Bethany L.; Chasson, Gregory S.

    2014-01-01

    Background Childhood maltreatment (CM) is a risk factor for subsequent intimate partner violence (IPV) in adulthood, with high rates of retrospectively reported CM among IPV victims and perpetrators. A theorized mechanism of the link between CM and IPV is dissociation. Dissociation may allow perpetrators of violence to remain emotionally distant from their behavior and minimize empathy toward those they victimize, enabling them to commit acts of violence similar to their own experiences. Indeed, elevated rates of dissociation and dissociative disorders (DD) have been found among IPV survivors and perpetrators. In addition, in pilot studies, DD clinicians have reported high levels of violent behavior among DD patients. Objective The present study investigates IPV among DD patients with Dissociative Identity Disorder and Dissociative Disorder Not Otherwise Specified, a group with CM rates of 80–95% and severe dissociative symptoms. Methods DD clinicians reported on rates of CM and IPV among 275 DD patients in outpatient treatment. DD patients also completed a self-report measure of dissociation. Analyses assessed the associations between CM typologies and IPV, as well as trait dissociation and IPV. Results Physical and emotional child abuse were associated with physical IPV, and childhood witnessing of domestic violence (DV) and childhood neglect were associated with emotional IPV. Conclusions The present study is the first to provide empirical support for a possible CM to adult IPV developmental trajectory among DD patients. Future research is needed to better understand the link between CM and IPV among those with trauma and DD. PMID:25279109

  19. Autocatalytic water dissociation on Cu(110) at near ambient conditions

    SciTech Connect

    Mulleregan, Alice; Andersson, Klas; Ketteler, Guido; Bluhm, Hendrik; Yamamoto, Susumu; Ogasawara, Hirohito; Pettersson, Lars G.M.; Salmeron, Miquel; Nilsson, Anders

    2007-05-16

    Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated based on X-ray photoelectron spectroscopy studies carried out in-situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H{sub 2}O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Broensted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.

  20. Psychometric validation of the State Scale of Dissociation (SSD).

    PubMed

    Krüger, Christa; Mace, Chris J

    2002-03-01

    Although dissociative phenomena are often transient features of mental states, existing measures of dissociation are designed to measure enduring traits. A new present-state self-report measure, sensitive to changes in dissociative states, was therefore developed and psychometrically validated. Fifty-six items were formulated to measure state features, and sorted according to seven subscales: derealization, depersonalization, identity confusion, identity alteration, conversion, amnesia and hypermnesia. The State Scale of Dissociation (SSD) was administered with other psychiatric scales (DES, BDI, BAI, SCI-PANSS) to 130 participants with DSM-IV major depressive disorder schizophrenia, alcohol withdrawal, dissociative disorders and controls. In these sample populations, the SSD was demonstrated as a valid and reliable measure of changes in and the severity of dissociative states. Discriminant validity, content, concurrent, predictive, internal criterion-related, internal construct and convergent validities, and internal consistency and split-half reliability were confirmed statistically. Clinical observations of dissociative states, and their comorbidity with symptoms of depression and psychotic illness, were confirmed empirically. The SSD, an acceptable, valid and reliable scale measuring state features of dissociation at the time of completion, was obtained. This is a prerequisite for further investigation of correlations between changes in dissociative states and concurrent physiological parameters. PMID:12006198

  1. The vibrational dynamics of 3D HOCl above dissociation

    NASA Astrophysics Data System (ADS)

    Lin, Yi-Der; Reichl, L. E.; Jung, Christof

    2015-03-01

    We explore the classical vibrational dynamics of the HOCl molecule for energies above the dissociation energy of the molecule. Above dissociation, we find that the classical dynamics is dominated by an invariant manifold which appears to stabilize two periodic orbits at energies significantly above the dissociation energy. These stable periodic orbits can hold a large number of quantum states and likely can support a significant quasibound state of the molecule, well above the dissociation energy. The classical dynamics and the lifetime of quantum states on the invariant manifold are determined.

  2. The Vibrational Dynamics of 3D HOCl Above Dissociation

    NASA Astrophysics Data System (ADS)

    Lin, Yi-Der; Reichl, Linda; Jung, Christof

    2015-03-01

    We have analyzed the vibrational dynamics of HOCl above dissociation using a 3D energy surface which governs the vibrational dynamics of HOCl above dissociation. The dynamics is dominated by an invariant manifold which is transversally unstable for small spacing between Cl and HO complex, and stable for large spacing. Above dissociation, the InM separates two mirror image periodic orbits, embedded in a large chaotic sea, that can hold a large number of quantum states. These periodic orbits have the capability of forming significant quasibound states of the molecule above dissociation. Welch Foundation.

  3. The vibrational dynamics of 3D HOCl above dissociation

    SciTech Connect

    Lin, Yi-Der; Reichl, L. E.; Jung, Christof

    2015-03-28

    We explore the classical vibrational dynamics of the HOCl molecule for energies above the dissociation energy of the molecule. Above dissociation, we find that the classical dynamics is dominated by an invariant manifold which appears to stabilize two periodic orbits at energies significantly above the dissociation energy. These stable periodic orbits can hold a large number of quantum states and likely can support a significant quasibound state of the molecule, well above the dissociation energy. The classical dynamics and the lifetime of quantum states on the invariant manifold are determined.

  4. Dissociation curves of diatomic molecules: A DC-DFT study

    SciTech Connect

    Sim, Eunji; Kim, Min-Cheol; Burke, Kieron

    2015-12-31

    We investigate dissociation of diatomic molecules using standard density functional theory (DFT) and density-corrected density functional theory (DC-DFT) compared with CCSD(T) results as reference. The results show the difference between the HOMO values of dissociated atomic species often can be used as an indicator whether DFT would predict the correct dissociation limit. DFT predicts incorrect dissociation limits and charge distribution in molecules or molecular ions when the fragments have large HOMO differences, while DC-DFT and CCSD(T) do not. The criteria for large HOMO difference is about 2 ∼ 4 eV.

  5. Dissociability of free and peptidyl-tRNA bound ribosomes.

    PubMed

    Surguchov, A P; Fominykch, E S; Lyzlova, L V

    1978-06-16

    The influence of peptidyl-tRNA on the dissociation of yeast 80 S ribosomes into subunits was studied. For this purpose temperature-sensitive (ts) suppressor strain of yeast Saccharomyces cervisiae carrying a defect in peptide chain termination was used. It was found that peptidyl-tRNA did not influence the dissociation of ribosomes either at high salt concentration or in the presence of dissociation factor (DF) from yeast. After dissociation of yeast ribosomes in 0.5 M KCl, peptidyl-tRNA remains bound to the 60 S subunit. Some characteristics of the termination process and release of nascent polypeptides from yeast ribosomes are discussed. PMID:355860

  6. Controls on Gas Hydrate Formation and Dissociation

    SciTech Connect

    Miriam Kastner; Ian MacDonald

    2006-03-03

    The main objectives of the project were to monitor, characterize, and quantify in situ the rates of formation and dissociation of methane hydrates at and near the seafloor in the northern Gulf of Mexico, with a focus on the Bush Hill seafloor hydrate mound; to record the linkages between physical and chemical parameters of the deposits over the course of one year, by emphasizing the response of the hydrate mound to temperature and chemical perturbations; and to document the seafloor and water column environmental impacts of hydrate formation and dissociation. For these, monitoring the dynamics of gas hydrate formation and dissociation was required. The objectives were achieved by an integrated field and laboratory scientific study, particularly by monitoring in situ formation and dissociation of the outcropping gas hydrate mound and of the associated gas-rich sediments. In addition to monitoring with the MOSQUITOs, fluid flow rates and temperature, continuously sampling in situ pore fluids for the chemistry, and imaging the hydrate mound, pore fluids from cores, peepers and gas hydrate samples from the mound were as well sampled and analyzed for chemical and isotopic compositions. In order to determine the impact of gas hydrate dissociation and/or methane venting across the seafloor on the ocean and atmosphere, the overlying seawater was sampled and thoroughly analyzed chemically and for methane C isotope ratios. At Bush hill the pore fluid chemistry varies significantly over short distances as well as within some of the specific sites monitored for 440 days, and gas venting is primarily focused. The pore fluid chemistry in the tub-warm and mussel shell fields clearly documented active gas hydrate and authigenic carbonate formation during the monitoring period. The advecting fluid is depleted in sulfate, Ca Mg, and Sr and is rich in methane; at the main vent sites the fluid is methane supersaturated, thus bubble plumes form. The subsurface hydrology exhibits both

  7. Products of Dissociative Recombination in the Ionosphere

    NASA Technical Reports Server (NTRS)

    Cosby, Philip

    1996-01-01

    SRI International undertook a novel experimental measurement of the product states formed by dissociative recombination (DR) of O2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and rovibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates. For a molecular ion such as O2(+), the dissociation recombination reaction is (1) O2(+) + e yields O + O + W. The atomic products of this reaction, in this case two oxygen atoms, can be produced in a variety of excited states and with a variety of kinetic energies, as represented by W in Eq. (1). These atoms are not only active in the neutral chemistry of the ionosphere, but are also especially important because their optical emissions are often used to infer in situ concentrations of the parent molecular ion and ambient electron densities. Many laboratory measurements have been made of DR reaction rates under a wide range of electron temperatures, but very little is known about the actual distributions among the final states of the atomic products. This lack of knowledge seriously limits the validity and effectiveness of efforts to model both natural and man-made ionospheric disturbances. Bates recently identified major deficiencies in the currently accepted branching ratios for O2(+) as they relate to blue and green line emission measurements in the nocturnal F-region. During our two-year effort, we partially satisfied our ambitious goals. We constructed and operated a variable pressure, electron-impact ion source and a high pressure, hollow-cathode discharge ion

  8. Acetylated histone H3 increases nucleosome dissociation

    NASA Astrophysics Data System (ADS)

    Simon, Marek; Manohar, Mridula; Ottesen, Jennifer; Poirier, Michael

    2009-03-01

    Chromatin's basic unit structure is the nucleosome, i.e. genomic DNA wrapped around a particular class of proteins -- histones -- which due to their physical hindrance, block vital biological processes, such as DNA repair, DNA replication, and RNA transcription. Histone post-translational modifications, which are known to exist in vivo, are hypothesized to regulate these biological processes by directly altering DNA-histone interactions and thus nucleosome structure and stability. Using magnetic tweezers technique we studied the acetylation of histone H3 in the dyad region, i.e. at K115 and K122, on reconstituted arrays of nucleosomes under constant external force. Based on the measured increase in the probability of dissociation of modified nucleosomes, we infer that this double modification could facilitate histone chaperone mediated nucleosome disassembly in vivo.

  9. Dissociative electron attachment studies on acetone

    SciTech Connect

    Prabhudesai, Vaibhav S. Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E.

    2014-10-28

    Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0–20 eV. H{sup −} is found to be the most dominant fragment followed by O{sup −} and OH{sup −} with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H{sup −} and O{sup −} fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

  10. Molecular Dissociation Induced by Electron Collisions

    NASA Astrophysics Data System (ADS)

    Wolf, Andreas

    2009-05-01

    Free electrons can efficiently break molecules or molecular ions in low-energy collisions by the processes of dissociative recombination or attachment. These processes make slow electrons efficient chemical agents in many environments. For dissociative recombination, in particular, studies of the underlying reaction paths and mechanisms have become possible on a uniquely elementary level in recent years both for theory and experiment. On the experimental side, collisions can be prepared at resolved collision energies down to the meV (10 Kelvin) level, increasingly gaining control also over the initial molecular quantum level, and individual events are detected and kinematically analyzed by fast-beam coincidence fragment imaging. Experiments are reported from the ion cooler ring TSR in Heidelberg. Stored beams of molecular ions cooled in their external and internal degrees of freedom are collinearly merged with intense and cold electron beams from cryogenic GaAs photocathodes, recently shown to yield fast cooling of the center-of-mass motion also for heavy and correspondingly slow molecular ion beams. To reconstruct the molecular fragmentation events multiparticle imaging can now be used systematically with collision energies set a wide range, especially aiming at specific electron capture resonances. Thus, for CF^+ it is found that the electronic state of the C fragment (^3P or ^1D) switches resonantly when the collision energy is changed by only a small fraction. As a new powerful tool, an energy-sensitive multi-strip surface-barrier detector (EMU) has been set up to measure with near-unity efficiency the masses of all fragments together with their hit positions in high-multiplicity events. Among many uses, this device allows internal molecular excitations to be derived for individual chemical channels in polyatomic fragmentation. New results will be presented in particular on the breakup of the hydronium ion (D3O^+).