Determining the composition of the vacuum-liquid interface in ionic-liquid mixtures.

The vacuum-liquid interfaces of a number of ionic-liquid mixtures have been investigated using the combination of reactive-atom scattering with laser-induced fluorescence detection (RAS-LIF), selected surface tension measurements, and molecular dynamics (MD) simulations. The mixtures are based on the widespread 1-alkyl-3-methylimidazolium ([Cnmim]+) cation, including mixed cations which differ in chain length or chemical functionality with a common anion; and different anions for a common cation. RAS-LIF results imply that the surface compositions exhibit a general form of non-stoichiometric behaviour that mimics the well-known Henry's and Raoult's laws at low and high mole fraction, respectively. The extended Langmuir model provides a moderately good single-parameter fit, but higher-order terms are required for an accurate description. The quantitative relationship between RAS-LIF and surface tension, which probes the surface composition only indirectly, is explored for mixtures of [C2mim]+ and [C12mim]+ with a common bis(trifluoromethylsulfonyl)imide ([NTf2]-) anion. Extended Langmuir model fits to surface tension data are broadly consistent with those to RAS-LIF; however, several other common approaches to extracting surface compositions from measured surface tensions result in much larger discrepancies. MD simulations suggest that RAS-LIF faithfully reports on the alkyl-chain exposure at the surface, which is only subtly modified by composition-dependent structural reorganisation.

Parity-dependent oscillations in collisional polarization transfer: CN(A²Π, v = 4) + Ar.

We report the first systematic experimental and theoretical study of the state-to-state transfer of rotational angular momentum orientation in a (2)Π-rare gas system. CN(X(2)Σ(+)) was produced by pulsed 266 nm photolysis of ICN in a thermal bath (296 K) of Ar collider gas. A pulsed circularly polarized tunable dye laser prepared CN(A(2)Π, v = 4) in two fully state-selected initial levels, j = 6.5 F1e and j = 10.5 F2f, with a known laboratory-frame orientation. Both the prepared levels and a range of product levels, j' F1e and j' F2f, were monitored using the circular polarized output of a tunable diode laser via cw frequency-modulated (FM) spectroscopy in stimulated emission on the CN(A-X) (4,2) band. The FM Doppler lineshapes for co-rotating and counter-rotating pump-and-probe geometries reveal the time-dependence of the populations and orientations. Kinetic fitting was used to extract the state-to-state population transfer rate constants and orientation multipole transfer efficiencies (MTEs), which quantify the degree of conservation of initially prepared orientation in the product level. Complementary full quantum scattering (QS) calculations were carried out on recently computed ab initio potential energy surfaces. Collision-energy-dependent tensor cross sections for ranks K = 0 and 1 were computed for transitions from both initial levels to all final levels. These quantities were integrated over the thermal collision energy distribution to yield predictions of the experimentally observed state-to-state population transfer rate constants and MTEs. Excellent agreement between experiment and theory is observed for both measured quantities. Dramatic oscillations in the MTEs are observed, up to and including changes in the sign of the orientation, as a function of even/odd Δj within a particular spin-orbit and e/f manifold. These oscillations, along with those also observed in the state-to-state rate constants, reflect the rotational parity of the final level. In general, parity-conserving collisions conserve rotational orientation, while parity-changing collisions result in large changes in the orientation. The QS calculations show that the dynamics of the collisions leading to these different outcomes are fundamentally different. We propose that the origin of this behavior lies in interferences between collisions that sample the even and odd-λ terms in the angular expansions of the PESs.

Depolarization of rotational angular momentum in CN(A2Π, v = 4) + Ar collisions.

Angular momentum depolarization and population transfer in CN(A(2)Π, v = 4, j, F(1)e) + Ar collisions have been investigated both experimentally and theoretically. Ground-state CN(X(2)Σ(+)) molecules were generated by pulsed 266-nm laser photolysis of ICN in a thermal (nominally 298 K) bath of the Ar collision partner at a range of pressures. The translationally thermalized CN(X) radicals were optically pumped to selected unique CN(A(2)Π, v = 4, j = 2.5, 3.5, 6.5, 11.5, 13.5, and 18.5, F(1)e) levels on the A-X (4,0) band by a pulsed tunable dye laser. The prepared level was monitored in a collinear geometry by cw frequency-modulated (FM) spectroscopy in stimulated emission on the CN(A-X) (4,2) band. The FM lineshapes for co- and counter-rotating circular pump and probe polarizations were analyzed to extract the time dependence of the population and (to a good approximation) orientation (tensor rank K = 1 polarization). The corresponding parallel and perpendicular linear polarizations yielded population and alignment (K = 2). The combined population and polarization measurements at each Ar pressure were fitted to a 3-level kinetic model, the minimum complexity necessary to reproduce the qualitative features of the data. Rate constants were extracted for the total loss of population and of elastic depolarization of ranks K = 1 and 2. Elastic depolarization is concluded to be a relatively minor process in this system. Complementary full quantum scattering (QS) calculations were carried out on the best previous and a new set of ab initio potential energy surfaces for CN(A)-Ar. Collision-energy-dependent elastic tensor and depolarization cross sections for ranks K = 1 and 2 were computed for CN(A(2)Π, v = 4, j = 1.5-10.5, F(1)e) rotational/fine-structure levels. In addition, integral cross sections for rotationally inelastic transitions out of these levels were computed and summed to yield total population transfer cross sections. These quantities were integrated over a thermal collision-energy distribution to yield the corresponding rate constants. A complete master-equation simulation using the QS results for the selected initial level j = 6.5 gave close, but not perfect, agreement with the near-exponential experimental population decays, and successfully reproduced the observed multimodal character of the polarization decays. On average, the QS population removal rate constants were consistently 10%-15% higher than those derived from the 3-level fit to the experimental data. The QS and experimental depolarization rate constants agree within the experimental uncertainties at low j, but the QS predictions decline more rapidly with j than the observations. In addition to providing a sensitive test of the achievable level of agreement between state-of-the art experiment and theory, these results highlight the importance of multiple collisions in contributing to phenomenological depolarization using any method sensitive to both polarized and unpolarized molecules in the observed level.

Rotationally elastic and inelastic dynamics of NO(X2Π, v = 0) in collisions with Ar.

A combined theoretical and experimental study of the depolarization of selected NO(X(2)Π, v = 0, j, F, ɛ) levels in collisions with a thermal bath of Ar has been carried out. Rate constants for elastic depolarization of rank K = 1 (orientation) and K = 2 (alignment) were extracted from collision-energy-dependent quantum scattering calculations, along with those for inelastic population transfer to discrete product levels. The rate constants for total loss of polarization of selected initial levels, which are the sum of elastic depolarization and population transfer contributions, were measured using a two-color polarization spectroscopy technique. Theory and experiment agree qualitatively that the rate constants for total loss of polarization decline modestly with j, but the absolute values differ by significantly more than the statistical uncertainties in the measurements. The reasons for this discrepancy are as yet unclear. The lack of a significant K dependence in the experimental data is, however, consistent with the theoretical prediction that elastic depolarization makes only a modest contribution to the total loss of polarization. This supports a previous conclusion that elastic depolarization for NO(X(2)Π) + Ar is significantly less efficient than for the electronically closely related system OH(X(2)Π) + Ar [P. J. Dagdigian and M. H. Alexander, J. Chem. Phys. 130, 204304 (2009)].

Elastic depolarization of OH(A) by He and Ar: a comparative study.

Two color polarization spectroscopy has been employed to measure the collisional depolarization of OH(A(2)Sigma(+), v = 1) by He and Ar. Complementary experiments using Zeeman quantum beat spectroscopy have also been performed to determine separately the cross sections for rotational energy transfer (RET) out of selected rotational levels of OH(A, v = 0) + Ar, as well as those for elastic depolarization. This has been achieved by dispersing the emission, so as to observe a single fluorescence transition. Elastic depolarization of OH(A) by Ar is found to be significant with that for loss of rotational alignment exceeding that for loss of orientation. In the case of OH(A) + He, the polarization spectroscopy measurements suggest that elastic depolarization plays a relatively minor role in the loss of the polarization signal compared with RET. The experimental data for OH(A) + Ar are compared in detail with the results of quasi-classical trajectory calculations that accommodate the effects of electron spin. These classical calculations are assessed against the results obtained using full close-coupled open shell quantum mechanical scattering methods. Overall the level of agreement between the two experiments, and between experiment and theory, is very reasonable. Surprisingly, at low N the elastic depolarization cross sections for OH(A) + Ar are found to be quite similar in magnitude to those observed for OH(X) + Ar despite the fact that the well depth in the latter system is considerably smaller than that for OH(A)-Ar. However, for OH(A) + Ar the depolarization cross sections are insensitive to N in the range 1-14. It is proposed that this behavior partly reflects the relatively anisotropic nature of the potential energy surface, which exhibits deep wells of different depths at the two linear configurations OH(A)-Ar and Ar-OH(A), and partly the nature of elastic depolarizing collisions, which must occur with a velocity component perpendicular to the plane of rotation of the diatomic molecule.

Functional outcome and patient preferences following combined phaco-vitrectomy for macular hole without prone posturing.

BACKGROUND: Macular hole surgery varies widely regarding the duration of gas tamponade, the use of patient posturing post-operatively, and whether or not cataract extraction is undertaken at the same time. AIM: To analyse anatomical and functional success rate following macular hole surgery and to examine patient preferences regarding posturing and length of gas tamponade. MATERIALS AND METHODS: Study design. Prospective, interventional and non-comparative case series. PARTICIPANTS: Thirty patients with stage III and IV full-thickness macular hole who underwent macular hole repair during the period April 2005-January 2006.Intervention. All eyes underwent a standard three-port pars plana vitrectomy, removal of posterior vitreous, internal limiting membrane (ILM) peel, C3F8 gas tamponade, and cataract extraction with IOL implantation. Patients did not posture post-operatively.Outcome measures. Post-operative anatomic results, visual acuity, complications, patient preferences regarding surgical protocol, and subjective improvement in visual function. RESULTS: Patients were followed up post-operatively for 6 months. Primary anatomical hole closure was achieved in 96.7% eyes. Visual acuity improved in 83.8% patients. Two patients had raised intraocular pressure following surgery. A total of 96.9% of patients were happy with no posturing and a 2-month gas bubble. CONCLUSIONS: There is a high rate of anatomical and functional success in patients undergoing macular hole surgery without prone posturing. In our study, most patients preferred long-acting gas tamponade with no posturing over the option of posturing with short-acting gas tamponade.

An unusual maculopathy after routine cataract surgery.

AIMS: To report the presentation of apparent acute and transient vitreomacular traction causing reduction in visual acuity following routine cataract surgery. METHODS: A case series describing three patients that developed acute and transient vitreomacular traction following routine cataract surgery by experienced surgeons. No patients had any significant past medical or ophthalmic history. The patients presented shortly after surgery with reduction in visual acuity and dramatic optical coherence tomography (OCT) images suggesting vitreomacular traction. RESULTS: All three patients experienced spontaneous resolution of symptoms and clinical signs within the first few weeks after surgery. Two patients experienced continued mild metamorphopsia. CONCLUSION: To our knowledge, this is the first documented report of such cases with associated confirmation by OCT imaging.

Expanding role of local anaesthesia in vitreoretinal surgery.

PURPOSE: Local anaesthesia (LA) is increasingly common in vitreoretinal surgery. However, younger patients often have such surgery under general anaesthesia (GA). We reanalysed the anaesthetic practice for vitreoretinal surgery in our unit over a 19-month period. METHODS: A total of 1003 patients undergoing vitreoretinal surgery between August 2000 and February 2002 were studied. Type of surgery, patient pain score to anaesthesia and surgery, need for sedation and incidence of complications related to the local anaesthetic were recorded. Comparisons were made between this case series and previous data from our unit. RESULTS: In total, 920/1003 (91.7%) patients had LA. Total operations comprised 418 vitrectomies, 518 retinopexies with or without vitrectomy and 67 buckling procedures. More patients under the age of 35 years had LA than previously (60.2 vs 35.7%, P<0.001). In 920/920 (100%) of cases, LA was administered via intraconal injection, compared to 164/1221 (13.4%) of procedures previously. Significantly more patients under the age of 35 years required sedation (35.9%) than did older patients (19.2%). Overall, use of sedation was significantly increased since our previous study (20.2 vs 7.8%). Anaesthesia and surgery were well tolerated by patients. There were no cases of orbital haemorrhage or ocular perforation. Complications included bradycardia requiring atropine 1/920 (0.1%) and chemosis 88/920 (9.6%). CONCLUSIONS: LA is well tolerated and effective even in younger patients. Sedation may well be required in younger patients and for procedures involving scleral buckling. The main indication for GA was patient preference. Despite this, such patients accounted for only 5.2% of the total.

Effect of video display on the grading of diabetic retinopathy.

PURPOSE: Digital images are increasingly being used in ophthalmology. These may be viewed either on thin-film transistor (TFT) or on cathode-ray tube (CRT) displays. However, there is little data showing which is superior. In this study, we compared the performance of CRT and TFT displays for grading of both compressed and uncompressed images of diabetic retinopathy. METHODS: A total of 49 35 mm transparencies of diabetic retinopathy were scanned and compressed. The images comprised 17 with no retinopathy, eight with background, five with preproliferative, and 19 with proliferative retinopathy. Four levels of compression were used: 0, 70, 80, and 90%. A total of 196 randomised images were presented to two masked graders using both TFT and CRT displays under uniform lighting conditions, 2 months apart. The grade of retinopathy was assessed. Statistical analysis of grading accuracy was performed using receiver operator characteristic curves of sensitivity and specificity and the Stuart-Maxwell test for paired, nonparametric data. RESULTS: Both displays showed high sensitivity and specificity for the detection of any retinopathy. For the specific grade of retinopathy, the CRT performed slightly better with a sensitivity of 0.80 for uncompressed images, compared with 0.75 using the TFT. Compression reduced these sensitivities to 0.73 on the CRT and 0.63 on the TFT. Grading of uncompressed images magnified to four times their original size was more accurate on the TFT. CONCLUSIONS: Grading on both displays met sensitivity and specificity criteria proposed by Diabetes UK (formerly British Diabetic Association) for screening of diabetic retinopathy. The CRT generally performed slightly better than the TFT in relation to the detection of the specific grade of retinopathy.

A comparison of stereoscopic and monoscopic evaluation of optic disc topography using a digital optic disc stereo camera.

AIMS: To compare stereophotographic and monophotographic optic disc assessments made using a digital optic disc stereo camera. METHODS: Stereo digital optic disc photographs of 150 selected patients who had presented to a glaucoma clinic were assessed by two masked observers on separate occasions using (1) the stereophotographs and a stereoviewer, (2) a single image from the same stereopair. Results were analysed for both right and left eyes separately. 95% tolerance limits for change (TC) and intraclass correlation coefficients (ICC) were calculated and a multivariate analysis using a general linear model for repeated measures was performed. RESULTS: A total of 201 optic disc images of 150 patients (84 females, 108 left eyes) were analysed. Mean age of patients was 64 years. The results for right eyes are as follows (similar results were obtained for left eyes). Intraobserver (stereoscopic compared to monoscopic) measurements of: horizontal cup:disc ratios (CDR), ICC = 0.5995 and 0.7269, TC = 34% and 27%; vertical CDR, ICC = 0.8298 and 0.817, TC = 25% and 27%; area CDR, ICC = 0.7757 and 0.8259, TC = 28% and 25%; circumference CDR, ICC = 0.7618 and 0.8103, TC = 28% and 25%. Interobserver measurements of: horizontal CDR, ICC stereoscopic (SS) = 0.7287; monoscopic (MS) = 0.5030; TC SS = 30%; MS = 32%; vertical CDR, ICC SS = 0.8439; MS = 0.7106; TC SS = 25%; MS = 31%; area CDR, ICC SS = 0.8392; MS = 0.6276; TC SS = 26%; MS = 32%; circumference CDR, ICC SS = 0.8433; MS = 0.6438, TC SS = 26%; MS = 31%. Systematic bias between observers and between methods was within acceptable limits. CONCLUSIONS: This study using a digital stereo camera indicates that there may be little benefit of stereoscopic imaging over monoscopic imaging despite demonstrating small but inconsistent differences between both observers and methods.

Effect of digital image compression on screening for diabetic retinopathy.

BACKGROUND/AIMS: Digital imaging is widely used for diabetic retinopathy screening. The storage and transmission of digital images can be facilitated by image compression. The authors aimed to assess the effect of image compression on the accuracy of grading diabetic retinopathy. METHODS: Forty nine 35 mm transparencies (17 with no retinopathy, eight with background, five with preproliferative, and 19 with proliferative retinopathy) were digitised and subjected to JPEG compression by 90%, 80%, 70%, and 0%. The 196 images were randomised and graded on a portable computer. Two masked graders assessed the images for grade of retinopathy and image quality (0-10). The sensitivity and specificity of retinopathy grading were calculated with a weighted kappa for grading agreement between levels of compression. RESULTS: The sensitivity of retinopathy grading was reduced by JPEG compression. At 90%, 80%, 70%, and 0% compression the sensitivities were 0.38, 0.50, 0.65, and 0.72, respectively; the specificity results were 1.00, 1.00, 0.83, and 0.84, respectively; and the weighted kappa scores were 0.60, 0.75, 0.77, and 0.84, respectively. The quality scores for 90%, 80%, 70%, 0% compression were 2.9 (SD 1.1, 95% CI; 2.7-3.2), 4.6 (SD 1.1, 95% CI; 3.0-5.6), 5.8 (SD1.5, 95% CI 5.0-6.6), 6.3 (SD1.4, 95% CI; 5.4-7.2) (p<0.01 for each intergroup comparison). CONCLUSION: The results demonstrate significant loss of sensitivity to the features of diabetic retinopathy with JPEG compression; this was compounded by the thin film transistor (TFT) screen. The authors found the quality of uncompressed images on TFT screens too poor to give grading sensitivities which reach current guidelines for diabetic retinopathy screening.