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1.
Int J Nurs Stud ; 148: 104608, 2023 Dec.
Article En | MEDLINE | ID: mdl-37801938

INTRODUCTION: Emergency departments play a critical role in healthcare systems internationally. Visits for emergency care continue to increase, related to poor access to primary care, the COVID-19 pandemic, and health human resource issues. International literature shows similar stressors in the emergency department. Extended wait times to see health providers lead to poor outcomes, and innovative models of care are needed to address emergency department overcrowding and to meet the needs of patients. Advanced practice nurses have the expertise and scope of practice to optimize and address primary and acute care needs and could be further integrated into the emergency healthcare systems. It is unclear what and how advanced practice nurses are functioning in emergency departments to improve patient and organization outcomes. METHODS: This scoping review was a comprehensive search of MEDLINE, EMCARE, EMBASE, Cumulative Index to Nursing and Allied Health Literature, and gray literature. Authors developed inclusion and exclusion criteria, performed title and abstract screening, and full text screening using review software. Data about models of care with advanced practice nurses were extracted and organized to understand patient, provider, and organizational outcomes. We also extracted information about the development and implementation of roles. RESULTS: Of the 6780 records identified, 76 met inclusion criteria. Emergency department models of care, mainly using nurse practitioners, include fast-track, generalized emergency, minor injury, orthopedics, pediatrics, geriatrics, specific populations, and triage. Reported patient outcomes include improvement in key metrics specific to emergency departments, such as total length of stay, wait times to be seen by a provider, left without being seen rates, treatment for pain, costs, and resource use. When comparing nurse practitioners to other providers, outcomes were similar or better for patient and organizational outcomes. DISCUSSION: Various models of care utilizing advanced practice nurses in emergency departments are present internationally and information about how they are developed, integrated, and utilized provides practical information to support and sustain new roles. There is an opportunity to expand the use of these roles into emergency departments as the nurse practitioner scope of practice grows. Given the current crisis across healthcare systems, there is need for innovation, and improving delivery of emergency services with these advanced practice nursing models of care can help to address important health policy priorities in Canada and other countries. TWEETABLE ABSTRACT: Advanced Practice Nurse models of care in emergency - Improved outcomes for patients and organizations - A review of the literature. @SamanthaH_RN.


Advanced Practice Nursing , Humans , Child , Pandemics , Delivery of Health Care , Triage , Emergency Service, Hospital
2.
Nurs Leadersh (Tor Ont) ; 36(1): 16-32, 2023 Apr.
Article En | MEDLINE | ID: mdl-37552515

The retention of Canada's advanced practice nurses (APNs), including clinical nurse specialists and nurse practitioners, is a national health human resources issue. APNs are essential within the Canadian healthcare workforce for meeting patient and population health needs, often in underserved communities. A shortage of APNs will exacerbate barriers to access to care for patients across sectors, including primary, acute, long-term and transitional care settings. This paper provides highlights from literature reporting on the state of APN human resources in Canada, including influential barriers and facilitators, and recommendations for retaining these important leaders in the healthcare workforce.


Advanced Practice Nursing , Nurse Practitioners , Humans , Canada , Workforce , Health Workforce
3.
Int J Comput Assist Radiol Surg ; 17(9): 1745-1750, 2022 Sep.
Article En | MEDLINE | ID: mdl-35511395

PURPOSE: NousNav is a complete low-cost neuronavigation system that aims to democratize access to higher-quality healthcare in lower-resource settings. NousNav's goal is to provide a model for local actors to be able to reproduce, build and operate a fully functional neuronavigation system at an affordable cost. METHODS: NousNav is entirely open source and relies on low-cost off-the-shelf components, which makes it easy to reproduce and deploy in any region. NousNav's software is also specifically devised with the low-resource setting in mind. RESULTS: It offers means for intuitive intraoperative control. The designed interface is also clean and simple. This allows for easy intraoperative use by either the practicing clinician or a nurse. It thus alleviates the need for a dedicated technician for operation. CONCLUSION: A prototype implementation of the design was built. Hardware and algorithms were designed for robustness, ruggedness, modularity, to be standalone and data-agnostic. The built prototype demonstrates feasibility of the objectives.


Neuronavigation , Software , Algorithms , Humans
4.
Can J Diabetes ; 46(1): 84-98, 2022 Feb.
Article En | MEDLINE | ID: mdl-34053879

OBJECTIVES: Workplace type 2 diabetes (T2D) prevention programs vary in intervention, delivery and methodologic approaches. Using predetermined criteria, we evaluated the effect and implementation of workplace interventions to prevent T2D. METHODS: We searched Embase, MEDLINE and Cochrane Central Register of Controlled Trials databases from January 2000 to June 2020 to overlap with the launch of the Diabetes Prevention Program (DPP) in 2002. Two reviewers independently screened and extracted data from eligible controlled trials. RESULTS: Five trials met the inclusion criteria, which included 1,494 adult participants; 791 (53%) were randomized to workplace interventions and 703 to usual workplace approaches. Pooled analysis showed that, when compared with controls, the participants in DPP-based interventions were 3.85 more likely to show a weight loss of ≥5% (4 randomized controlled trials [RCTs]; risk ratio [RR]=3.85; 95% confidence interval [CI], 1.58 to 9.38; p<0.05), and 9.36-fold more likely to show a weight loss of 7% (2 RCTs; RR=9.36; 95% CI, 2.31 to 37.97; p<0.05). The pooled evidence showed significant difference in effect favouring DPP-based interventions as compared with controls (4 RCTs; standardized mean difference, 0.38; 95% CI, 0.21 to 0.55; p<0.05). All included studies did have 3 common elements of the DPP: coaches, a focus on 7% weight loss and an increase in physical activity to a minimum of 150 min/week. CONCLUSIONS: DPP interventions in the workplace continue to be an important and worthwhile strategy. Our review shows that such programs reveal promising evidence for weight loss and improved physical activities with less intensive and structured supports.


Diabetes Mellitus, Type 2 , Workplace , Adult , Diabetes Mellitus, Type 2/epidemiology , Diabetes Mellitus, Type 2/prevention & control , Exercise , Humans , Randomized Controlled Trials as Topic
5.
Plast Reconstr Surg ; 146(3): 314e-323e, 2020 09.
Article En | MEDLINE | ID: mdl-32459727

BACKGROUND: Current methods to analyze three-dimensional photography do not quantify intracranial volume, an important metric of development. This study presents the first noninvasive, radiation-free, accurate, and reproducible method to quantify intracranial volume from three-dimensional photography. METHODS: In this retrospective study, cranial bones and head skin were automatically segmented from computed tomographic images of 575 subjects without cranial abnormality (average age, 5 ± 5 years; range, 0 to 16 years). The intracranial volume and the head volume were measured at the cranial vault region, and their relation was modeled by polynomial regression, also accounting for age and sex. Then, the regression model was used to estimate the intracranial volume of 30 independent pediatric patients from their head volume measured using three-dimensional photography. Evaluation was performed by comparing the estimated intracranial volume with the true intracranial volume of these patients computed from paired computed tomographic images; two growth models were used to compensate for the time gap between computed tomographic and three-dimensional photography. RESULTS: The regression model estimated the intracranial volume of the normative population from the head volume calculated from computed tomographic images with an average error of 3.81 ± 3.15 percent (p = 0.93) and a correlation (R) of 0.96. The authors obtained an average error of 4.07 ± 3.01 percent (p = 0.57) in estimating the intracranial volume of the patients from three-dimensional photography using the regression model. CONCLUSION: Three-dimensional photography with image analysis provides measurement of intracranial volume with clinically acceptable accuracy, thus offering a noninvasive, precise, and reproducible method to evaluate normal and abnormal brain development in young children. CLINICAL QUESTION/LEVEL OF EVIDENCE: Diagnostic, V.


Imaging, Three-Dimensional , Photography/methods , Skull/anatomy & histology , Skull/diagnostic imaging , Tomography, X-Ray Computed , Adolescent , Child , Child, Preschool , Female , Humans , Infant , Male , Organ Size , Retrospective Studies
6.
Article En | MEDLINE | ID: mdl-31474785

Ultrasound (US)-guided renal biopsy is a critically important tool in the evaluation and management of non-malignant renal pathologies with diagnostic and prognostic significance. It requires a good biopsy technique and skill to safely and consistently obtain high yield biopsy samples for tissue analysis. This project aims to develop a virtual trainer to help clinicians to improve procedural skill competence in real-time ultrasound-guided renal biopsy. This paper presents a cost-effective, high-fidelity trainer built using low-cost hardware components and open source visualization and interactive simulation libraries: interactive medical simulation toolkit (iMSTK) and 3D Slicer. We used a physical mannequin to simulate the tactile feedback that trainees experience while scanning a real patient and to provide trainees with spatial awareness of the US scanning plane with respect to the patient's anatomy. The ultrasound probe and biopsy needle were modeled using commonly used clinical tools and were instrumented to communicate with the simulator. 3D Slicer was used to visualize an image sliced from a pre-acquired 3-D ultrasound volume based on the location of the probe, with a realistic needle rendering. The simulation engine in iMSTK modeled the interaction between the needle and the virtual tissue to generate visual deformations on the tissue and tactile forces on the needle which are transmitted to the needle that the user holds. Initial testing has shown promising results with respect to quality of simulated images and system responsiveness. Further evaluation by clinicians is planned for the next stage.

7.
Annu Int Conf IEEE Eng Med Biol Soc ; 2018: 5802-5805, 2018 Jul.
Article En | MEDLINE | ID: mdl-30441654

Upper airway obstructions leading todifficulty breathing are significant problems that often require surgery to improve patient quality of life. However, these surgeries often have poor outcomes with little symptom improvement. This paper outlines the design of an interactive, patient-specific virtual surgical planning system that uses patient CT scans to generate three-dimensional representations of the airways and incorporates computational fluid dynamics (CFD) as a part of the surgical planning process. Individualized virtual surgeries can be performed by editing these models, which are then analyzed using CFD to compare pre- and post- surgery flow characteristics to assess patient symptom improvement. The prototype system shows significant promise by being intuitive, interactive, with a potential fast flow solver that provides near real-time feedback to the clinician.


Image Interpretation, Computer-Assisted , Imaging, Three-Dimensional , Nasal Obstruction/surgery , Surgical Procedures, Operative , Computer Simulation , Humans , Hydrodynamics , User-Computer Interface
8.
Hum Factors ; 59(7): 1128-1138, 2017 11.
Article En | MEDLINE | ID: mdl-28771376

Objective These studies used threshold and slant-matching tasks to assess and quantitatively measure human perception of 3-D planar images viewed through a stereomicroscope. The results are intended for use in developing augmented-reality surgical aids. Background Substantial research demonstrates that slant perception is performed with high accuracy from monocular and binocular cues, but less research concerns the effects of magnification. Viewing through a microscope affects the utility of monocular and stereo slant cues, but its impact is as yet unknown. Method Participants performed in a threshold slant-detection task and matched the slant of a tool to a surface. Different stimuli and monocular versus binocular viewing conditions were implemented to isolate stereo cues alone, stereo with perspective cues, accommodation cue only, and cues intrinsic to optical-coherence-tomography images. Results At magnification of 5x, slant thresholds with stimuli providing stereo cues approximated those reported for direct viewing, about 12°. Most participants (75%) who passed a stereoacuity pretest could match a tool to the slant of a surface viewed with stereo at 5x magnification, with mean compressive error of about 20% for optimized surfaces. Slant matching to optical coherence tomography images of the cornea viewed under the microscope was also demonstrated. Conclusion Despite the distortions and cue loss introduced by viewing under the stereomicroscope, most participants were able to detect and interact with slanted surfaces. Application The experiments demonstrated sensitivity to surface slant that supports the development of augmented-reality systems to aid microscope-aided surgery.


Depth Perception/physiology , Microscopy , Visual Perception/physiology , Adult , Humans
9.
Appl Opt ; 53(24): 5421-4, 2014 Aug 20.
Article En | MEDLINE | ID: mdl-25321114

This paper describes a projection system for augmenting a scanned laser projector to create very small, very bright images for use in a microsurgical augmented reality system. Normal optical design approaches are insufficient because the laser beam profile differs optically from the aggregate image. We propose a novel arrangement of two lens groups working together to simultaneously adjust both the laser beam of the projector (individual pixels) and the spatial envelope containing them (the entire image) to the desired sizes. The present work models such a system using paraxial beam equations and ideal lenses to demonstrate that there is an "in-focus" range, or depth of field, defined by the intersection of the resulting beam-waist radius curve and the ideal pixel radius for a given image size. Images within this depth of field are in focus and can be adjusted to the desired size by manipulating the lenses.


Imaging, Three-Dimensional/instrumentation , Lasers , Lighting/instrumentation , Microsurgery/instrumentation , Ophthalmologic Surgical Procedures/instrumentation , Surgery, Computer-Assisted/instrumentation , Tomography, Optical Coherence/instrumentation , Equipment Design , Equipment Failure Analysis
10.
J Chem Theory Comput ; 10(5): 2091-102, 2014 May 13.
Article En | MEDLINE | ID: mdl-26580536

Electron transfer reactions at electrochemical interfaces play a critical role in a wide range of catalytic processes. A key parameter in the rate constant expressions for such processes is the reorganization energy, which reflects the energetic cost of the solute and solvent rearrangements upon electron transfer. In this paper, we present dielectric continuum methods for calculating the solvent reorganization energy for electrochemical processes. We develop a method for calculating the electrochemical solvent reorganization energies with molecular-shaped cavities within the framework of the polarizable continuum model (PCM). The electronic and inertial responses of the solvent are separated according to their respective time scales, and two limiting cases of the relation between the solute and solvent electrons are examined. The effects of the electrode are included with the integral equations formalism PCM (IEF-PCM), in which the molecule-solvent boundary is treated explicitly, but the effects of the electrode-solvent boundary are included through an external Green's function. This approach accounts for the effects of detailed molecular charge redistribution in a molecular-shaped cavity, as well as the electronic and inertial solvent responses and the effects of the electrode. The calculated total reorganization energies are in reasonable agreement with experimental measurements for a series of electrochemical systems. Inclusion of the effects of the electrode is found to be essential for obtaining even qualitatively accurate solvent reorganization energies. These approaches are applicable to a wide range of systems and can be extended to include other types of boundaries, such as a self-assembled monolayer or double layer separating the electrode and the molecule.

11.
IEEE J Transl Eng Health Med ; 2: 2700109, 2014.
Article En | MEDLINE | ID: mdl-27170882

We present a novel device mounted on the fingertip for acquiring and transmitting visual information through haptic channels. In contrast to previous systems in which the user interrogates an intermediate representation of visual information, such as a tactile display representing a camera generated image, our device uses a fingertip-mounted camera and haptic stimulator to allow the user to feel visual features directly from the environment. Visual features ranging from simple intensity or oriented edges to more complex information identified automatically about objects in the environment may be translated in this manner into haptic stimulation of the finger. Experiments using an initial prototype to trace a continuous straight edge have quantified the user's ability to discriminate the angle of the edge, a potentially useful feature for higher levels analysis of the visual scene.

12.
Inorg Chem ; 52(7): 3643-52, 2013 Apr 01.
Article En | MEDLINE | ID: mdl-23477912

The nickel-based P2(Ph)N2(Bn) electrocatalysts comprised of a nickel atom and two 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane ligands catalyze H2 production in acetonitrile. Recent electrochemical experiments revealed a linear dependence of the Ni(II/I) reduction potential on pH with a slope of 57 mV/pH unit, implicating a proton-coupled electron transfer (PCET) process with the same number of electrons and protons transferred. The combined theoretical and experimental studies herein provide an explanation for this pH dependence in the context of the overall proposed catalytic mechanism. In the proposed mechanisms, the catalytic cycle begins with a series of intermolecular proton transfers from an acid to the pendant amine ligand and electrochemical electron transfers to the nickel center to produce the doubly protonated Ni(0) species, a precursor to H2 evolution. The calculated Ni(II/I) reduction potentials of the doubly protonated species are in excellent agreement with the experimentally observed reduction potential in the presence of strong acid, suggesting that the catalytically active species leading to the peak observed in these cyclic voltammetry (CV) experiments is doubly protonated. The Ni(I/0) reduction potential was found to be slightly more positive than the Ni(II/I) reduction potential, indicating that the Ni(I/0) reduction occurs spontaneously after the Ni(II/I) reduction, as implied by the experimental observation of a single CV peak. These results suggest that the PCET process observed in the CV experiments is a two-electron/two-proton process corresponding to an initial double protonation followed by two reductions. On the basis of the experimental and theoretical data, the complete thermodynamic scheme and the Pourbaix diagram were generated for this catalyst. The Pourbaix diagram, which identifies the most thermodynamically stable species at each reduction potential and pH value, illustrates that this catalyst undergoes different types of PCET processes for various pH ranges. These thermodynamic insights will aid in the design of more effective molecular catalysts for H2 production.

13.
J Phys Chem Lett ; 4(3): 542-6, 2013 Feb 07.
Article En | MEDLINE | ID: mdl-26281752

The design of hydrogen oxidation and production electrocatalysts is important for the development of alternative renewable energy sources. The overall objective is to maximize the turnover frequency and minimize the overpotential. We use computational methods to examine a variety of nickel-based molecular electrocatalysts with pendant amines. Our studies focus on the proton-coupled electron transfer (PCET) process involving electron transfer between the complex and the electrode and intramolecular proton transfer between the nickel center and the nitrogen of the pendant amine. The concerted PCET mechanism, which tends to require a lower overpotential, is favored by a smaller equilibrium Ni-N distance and a more flexible pendant amine ligand, thereby decreasing the energetic penalty for the nitrogen to approach the nickel center for proton transfer. Our calculations provide predictions about designing catalysts that incorporate these properties. These design principles will be useful for developing the next generation of hydrogen catalysts.

14.
Proc Natl Acad Sci U S A ; 109(39): 15663-8, 2012 Sep 25.
Article En | MEDLINE | ID: mdl-22529352

The design of molecular electrocatalysts for H(2) oxidation and production is important for the development of alternative renewable energy sources that are abundant, inexpensive, and environmentally benign. Recently, nickel-based molecular electrocatalysts with pendant amines that act as proton relays for the nickel center were shown to effectively catalyze H(2) oxidation and production. We developed a quantum mechanical approach for studying proton-coupled electron transfer processes in these types of molecular electrocatalysts. This theoretical approach is applied to a nickel-based catalyst in which phosphorous atoms are directly bonded to the nickel center, and nitrogen atoms of the ligand rings act as proton relays. The catalytic step of interest involves electron transfer between the nickel complex and the electrode as well as intramolecular proton transfer between the nickel and nitrogen atoms. This process can occur sequentially, with either the electron or proton transferring first, or concertedly, with the electron and proton transferring simultaneously without a stable intermediate. The electrochemical rate constants are calculated as functions of overpotential for the concerted electron-proton transfer reaction and the two electron transfer reactions in the sequential mechanisms. Our calculations illustrate that the concerted electron-proton transfer standard rate constant will increase as the equilibrium distance between the nickel and nitrogen atoms decreases and as the pendant amines become more flexible to facilitate the contraction of this distance with a lower energy penalty. This approach identifies the favored mechanisms under various experimental conditions and provides insight into the impact of substituents on the nitrogen and phosphorous atoms.


Models, Chemical , Protons , Renewable Energy , Catalysis , Electrochemical Techniques , Electron Transport , Nickel/chemistry , Oxidation-Reduction , Phosphorus/chemistry
15.
J Chem Phys ; 134(18): 184311, 2011 May 14.
Article En | MEDLINE | ID: mdl-21568510

A combined experimental and theoretical investigation of photodissociation dynamics of IBr(-) and IBr(-)(CO(2)) on the B ((2)Σ(1/2)(+)) excited electronic state is presented. Time-resolved photoelectron spectroscopy reveals that in bare IBr(-) prompt dissociation forms exclusively I∗ + Br(-). Compared to earlier dissociation studies of IBr(-) excited to the A' ((2)Π(1∕2)) state, the signal rise is delayed by 200 ± 20 fs. In the case of IBr(-)(CO(2)), the product distribution shows the existence of a second major (∼40%) dissociation pathway, Br∗ + I(-). In contrast to the primary product channel, the signal rise associated with this pathway shows only a 50 ± 20 fs delay. The altered product branching ratio indicates that the presence of one solvent-like CO(2) molecule dramatically affects the electronic structure of the dissociating IBr(-). We explore the origins of this phenomenon with classical trajectories, quantum wave packet studies, and MR-SO-CISD calculations of the six lowest-energy electronic states of IBr(-) and 36 lowest-energy states of IBr. We find that the CO(2) molecule provides sufficient solvation energy to bring the initially excited state close in energy to a lower-lying state. The splitting between these states and the time at which the crossing takes place depend on the location of the solvating CO(2) molecule.

16.
J Phys Chem A ; 114(42): 11337-46, 2010 Oct 28.
Article En | MEDLINE | ID: mdl-20712343

The role of laser pulse width as well as other quantum mechanical effects in the interpretation of the observed time-resolved photoelectron spectra (TRPES) of IBr(-) are investigated using conditions that are chosen to reproduce those used for the experimental study of Mabbs et al. [ J. Chem. Phys. 2005 , 122 , 174305 ]. In that study, it was shown that one could correlate shifts in the frequency of the maximum in signal as a function of time to differences between the potential energies of the electronic states that are accessed by the pump and probe lasers. While this classical picture is attractive, it is based on a single trajectory with an initial I-Br separation that is ∼0.3 Šlonger than the equilibrium value. In addition, it does not include the role of the pulse widths and other possible quantum effects. In the present work, the six lowest energy electronic states of IBr(-) were calculated at the MR-SO-CISD/aug-cc-pVDZ level of theory/basis set as a function of the I-Br distance. The TRPES of IBr(-) were calculated in three pulse regimes: an infinitesimally short pulse, an intermediate pulse that has a temporal full width at half-maximum (fwhm) of 300 fs, which was chosen to match the experimental value, and one that is 3 times longer than the experimental value. The resulting spectra are qualitatively different, and the sources of these differences are discussed. The intermediate pulse provides very good agreement with experiment with the introduction of no adjustable parameters. The origins of the features of the experimental signal are discussed in terms of this fully quantum mechanical picture.

17.
Science ; 328(5975): 220-4, 2010 Apr 09.
Article En | MEDLINE | ID: mdl-20203015

Chemical bond breaking involves coupled electronic and nuclear dynamics that can take place on multiple electronic surfaces. Here we report a time-resolved experimental and theoretical investigation of nonadiabatic dynamics during photodissociation of a complex of iodine monobromide anion with carbon dioxide [IBr-(CO2)] on the second excited (A') electronic state. Previous experimental work showed that the dissociation of bare IBr- yields only I- + Br products. However, in IBr-(CO2), time-resolved photoelectron spectroscopy reveals that a subset of the dissociating molecules undergoes an electron transfer from iodine to bromine 350 femtoseconds after the initial excitation. Ab initio calculations and molecular dynamics simulations elucidate the mechanism for this charge hop and highlight the crucial role of the carbon dioxide molecule. The charge transfer between two recoiling atoms, assisted by a single solvent-like molecule, provides a notable limiting case of solvent-driven electron transfer over a distance of 7 angstroms.

18.
J Phys Chem A ; 114(3): 1556-68, 2010 Jan 28.
Article En | MEDLINE | ID: mdl-20025227

Vibrational predissociation spectra of the argon-tagged halide monohydrates, X(-) .H(2)O.Ar (X = Cl, Br, or I), are recorded from approximately 800 to 3800 cm(-1) by monitoring the loss of the argon atom. We use this set of spectra to investigate how the spectral signatures of the hydrogen-bonding and large-amplitude hindered rotations of the water molecule are affected by incremental substitution of the hydrogen atoms by deuterium. All six vibrational modes of the X(-).H(2)O complexes are assigned through fundamental transitions, overtones, or combination bands. To complement the experimental study, harmonic and reduced-dimensional calculations of the vibrational spectra are performed based on the MP2/aug-cc-pVTZ level of theory and basis set. Comparison of these results with those from the converged six-dimensional calculations of Rheinecker and Bowman [J. Chem. Phys. 2006, 125, 133206.] show good agreement, with differences smaller than 30 cm(-1). The simpler method has the advantage that it can be readily extended to the heavier halides and was found to accurately recover the wide range of behaviors displayed by this series, including the onset of tunneling between equivalent minima arising from the asymmetrical (single ionic hydrogen-bonded) equilibrium structures of the complexes.

19.
J Phys Chem A ; 112(48): 12337-44, 2008 Dec 04.
Article En | MEDLINE | ID: mdl-18991426

Vibrational predissociation spectra of the F(-)(H(2)O) x Ar and F(-)(D(2)O) x Ar complexes are observed over a range of 600 to 3800 cm(-1), which include bands attributed to the fundamentals as well as the first two overtones of the vibrations primarily associated with the shared hydrogen. This information allows us to characterize both the extended potential surface confining the anionic H-bonded hydrogen and the degree to which this motion is coupled to the motions of other atoms in the complex. We analyze these new data with reduced dimensional treatments using explicit potential energy and electric dipole moment surfaces. The often employed one-dimensional treatment with fixed OF distance does not even qualitatively account for the observed isotope dependent level structures, but a simple extension to two dimensions, corresponding to the OF distance and the shared proton position, accurately recovers the observed spectra. The resulting two-dimensional wave functions are used to evaluate the extent of proton transfer in each vibrational level. The main conclusion of this work is that vibrational excitation of the shared proton can be regarded as optically driven, intracluster proton transfer.

20.
J Chem Phys ; 126(8): 084307, 2007 Feb 28.
Article En | MEDLINE | ID: mdl-17343448

We report the femtosecond nuclear dynamics of Cu(CD3OD) van der Waals clusters, investigated using photodetachment-photoionization spectroscopy. Photodetachment of an electron from Cu-(CD3OD) with a 150 fs, 398 nm laser pulse produces a vibrationally excited neutral complex that undergoes ligand reorientation and dissociation. The dynamics of Cu(CD3OD) on the neutral surface is interrogated by delayed femtosecond resonant two-photon ionization. Analysis of the resulting time-dependent signals indicates that the nascent Cu(CD3OD) complex dissociates on two distinct time scales of 3 and 30 ps. To understand the origins of the observed time scales, complimentary studies were performed. These included measurement of the photoelectron spectrum of Cu-(CD3OD) as well as a series of calculations of the structure and the electronic and vibrational energies of the anion and neutral complexes. Based on the comparisons of the experimental and calculated results for Cu(CD3OD) with those obtained from earlier studies of Cu(H2O), we conclude that the 3 ps time scale reflects the energy transfer from the rotation of CD3OD in the complex to the dissociation coordinate, while the 30 ps time scale reflects the energy transfer from the excited methyl torsion states to the dissociation coordinate.

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