Semiclassical Trajectory Studies of Reactive and Nonreactive Scattering of OH(A 2 Σ+ ) by H2 Based on an Improved Full-Dimensional Ab Initio Diabatic Potential Energy Matrix.

We present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2 Σ+ ) with H2 , and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2 O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching.

Homogeneous Catalytic CO2 Hydrogenation by [Fe]-Hydrogenase Bioinspired Complexes: A Computational Study.

Computational modeling at the DLPNO-CCSD(T)/CBS//M06-L/def2-TZVP level of theory was used to propose four different iron catalysts whose structures were inspired on the [Fe]-hydrogenase active site: [Fe(MePNNHNP)(acmp)] (C(1), MePNNHNP = 2,6-bis(dimethylphosphine), acmp = acylmethylpyridine), [Fe(CNNHNC)(acmp)] (C(2), CNNHNC = 2,6-bis(methylimidazol-2-ylidene)), [Fe(MePNNNP)(acmp)] (D(1), MePNNNP = 2,6-bis((dimethylphosphine)pyridine)), and [Fe(CNNNC)(acmp)] (D(2), CNNNC = 2,6-bis((methylimidazol-2-ylidene) pyridine)). Through these electronic structure calculations, the catalytic mechanism of the reaction was explored. The intermediates and transition states present along the reaction coordinate were identified and described as to their equilibrium geometries, vibrational frequencies, and energies. Quasi-harmonic corrections were performed considering conditions analogous to those used experimentally. To compare the catalytic activities of the studied catalysts, turnover frequencies (TOFs) were calculated. Based on the explored catalytic cycles and TOF values (D(1) > C(1) > D(2) > C(2)), the most suitable iron catalysts are those with tridentate phosphine pincer-type ligands coordinated to the metal center. These systems are new promising iron catalysts to promote the CO2 hydrogenation to formic acid without any use of bases or additives.

Protocol for optically pumping AlH+ to a pure quantum state.

We propose an optical pumping scheme to prepare trapped AlH+ molecules in a pure state, the stretched hyperfine state of the rovibronic ground manifold |X2Σ+, v = 0, N = 0 . Our scheme utilizes linearly-polarized and circularly-polarized fields of a broadband pulsed laser to cool the rotational degree of freedom and drive the population to the hyperfine state, respectively. We simulate the population dynamics by solving a representative system of rate equations that accounts for the laser fields, blackbody radiation, and spontaneous emission. In order to model the hyperfine structure, new hyperfine constants of the A2Π excited state were computed using a RASSCF wavefunction. We find that adding an infrared laser to drive the 1-0 vibrational transition within the X2Σ+ manifold accelerates the cooling process. The results show that, under optimal conditions, the population in the target state of the rovibronic ground manifold can reach 63% after 68 µs (330 ms) and 95% after 25 ms (1.2 s) with (without) the infrared laser.

Computational mechanistic investigation of the Fe + CO2→ FeO + CO reaction.

We report a computational study of the mechanism and determination of the rate constants of the Fe + CO2→ FeO + CO reaction, in the 1000-3000 K temperature range, at the CCSD(T)/CBS//B3LYP/def2-TZVP level of theory. The overall rate constant was obtained by a Kinetic Monte Carlo simulation. The calculated rate constant, at 2000 K, is 9.72 × 10-13 cm3 molecule-1 s-1, in agreement with experimental measurements: 2.97 × 10-13 cm3 molecule-1 s-1 [A. Giesen et al., Phys. Chem. Chem. Phys., 2002, 4, 3665] and 1.13 × 10-13 cm3 molecule-1 s-1 [V. N. Smirnov, Kinet. Catal., 2008, 49, 607]. Our study shows that this reaction follows a complex mechanism, with multiple reaction paths contributing to the overall rate, and that CCSD(T) accurately describes this transition metal reaction.

Photophysical properties and the NO photorelease mechanism of a ruthenium nitrosyl model complex investigated using the CASSCF-in-DFT embedding approach.

A complete state-averaged active space self-consistent field (SA-CASSCF) calculation by means of the SA-CASSCF(18,14)-in-BP86 Miller-Manby embedding approach was performed to explore the ground and excited electronic states of the trans-[RuCl(NO)(NH3)4]2+ complex. Insights into the NO photodissociation mechanism and Ru-NO bonding properties are provided. In addition, spin-orbit (SO) interactions were taken into account to describe and characterize the spin-forbidden transitions observed at the low-energy regions of the trans-[RuCl(NO)(NH3)4]2+ UV-Vis spectrum. The SA-CASSCF(18,14)-in-BP86 electronic spectrum is in great agreement with the experimental data of Schreiner [Schreiner et al., Inorg. Chem., 1972, 11, 880].

Energy disposal and thermal rate constants for the OH + HBr and OH + DBr reactions: quasiclassical trajectory calculations on an accurate potential energy surface.

We report reaction cross sections, energy disposal, and rate constants for the OH + HBr → Br + H2O and OH + DBr → Br + HDO reactions from quasiclassical trajectory calculations using an ab initio potential energy surface [ de Oliveira-Filho , A. G. S. ; Ornellas , F. R. ; Bowman , J. M. J. Phys. Chem. Lett. 2014 , 5 , 706 - 712 ]. Comparison with available experiments are made and generally show good agreement.

Thermal rate constants for the O(3P) + HBr and O(3P) + DBr reactions: transition-state theory and quantum mechanical calculations.

The O((3)P) + HBr → OH + Br and O((3)P) + DBr → OD + Br reactions are studied on a recent high-quality ab initio-based potential energy surface. Thermal rate constants over the 200-1000 K temperature range, calculated using variational transition-state theory (VTST) with the small-curvature tunneling (SCT) correction and quantum mechanical methods with the J-shifting approximation (QM/JS) for zero total angular momentum (J = 0), are reported. These results are compared to the available experimental data, which lie in the ranges of 221-554 and 295-419 K for O + HBr and O + DBr, respectively. The rate constants, in cm(3) molecule(-1) s(-1) and at 298 K, for the O + HBr reaction are 3.66 × 10(-14) for VTST, 3.80 × 10(-14) for QM/JS, and 3.66 × 10(-14) for the average of eight experimental measurements.

The surprising metastability of TeH2+.

A high-level ab initio investigation of a manifold of electronic states of the diatomic dication TeH(2+) is presented. Potential energy curves for both Λ + S and relativistic (Ω) states are constructed not only making evident the metastability of this system, but also the large energy splitting due to spin-orbit interactions. This effect is also very significant in the region close to the crossing of the (2)Π and (4)Σ(-) states, where avoided crossings between the Ω states have a relatively large impact on the height of the energy barriers. In contrast to TeH, with only two bound states (X1 (2)Π3∕2 and X2 (2)Π1∕2) below about 25,000 cm(-1), in the case of TeH(2+) a much richer energy profile is obtained indicating various possibilities of electronic transitions. Guided by the results of this study, the experimental characterization of these states is now a challenge to spectroscopists. Since close to the equilibrium region the double positive charge is centered on the tellurium atom, the binding in this system can be rationalized as a simple covalent bond between the pz and s orbitals of Te(2+) and H, respectively. As the internuclear distance increases, the electron affinity of Te(2+) overcomes that of H(+) and the system dissociates into two singly charged fragments. A simulation of the double ionization spectra complements the characterization of the electronic states, and results of a mass spectrometric investigation corroborates the predicted transient existence of this metastable species.

Postoperative vomiting in pediatric oncologic patients: prediction by a fuzzy logic model.

OBJECTIVE: To report a fuzzy logic mathematical model to predict postoperative vomiting (POV) in pediatric oncologic patients and compare with preexisting scores. BACKGROUND: Although POV has a high incidence in children and may decrease parental satisfaction after surgeries, there is only one specific score that predicts POV in children: the Eberhart's score. In this study, we report a fuzzy model that intends to predict the probability of POV in pediatric oncologic patients. Fuzzy logic is a mathematical theory that recognizes more than simple true and false values and takes into account levels of continuous variables such as age or duration of the surgery. The fuzzy model tries to account for subjectiveness in the variables. METHODS: Preoperative potential risk factors for POV in 198 children (0-19 year old) with malignancies were collected and analyzed. Data analysis was performed with the chi-square test and logistic regression to evaluate probable risk factors for POV. A system based on fuzzy logic was developed with the risk factors found in the logistic regression, and a computational interface was created to calculate the probability of POV. RESULTS: The model showed a good performance in predicting POV. After the analysis, the model was compared with Eberhart's score in the same population and showed a better performance. CONCLUSIONS: The fuzzy score can predict the chance of POV in children with cancer with good accuracy, allowing better planning for postoperative prophylaxis of vomiting. The computational interface is available for free download at the internet and is very easy to use.

Accurate ab initio potential energy surfaces for the 3A'' and 3A' electronic states of the O(3P)+HBr system.

In this work, we report the construction of potential energy surfaces for the (3)A('') and (3)A(') states of the system O((3)P) + HBr. These surfaces are based on extensive ab initio calculations employing the MRCI+Q/CBS+SO level of theory. The complete basis set energies were estimated from extrapolation of MRCI+Q/aug-cc-VnZ(-PP) (n = Q, 5) results and corrections due to spin-orbit effects obtained at the CASSCF/aug-cc-pVTZ(-PP) level of theory. These energies, calculated over a region of the configuration space relevant to the study of the reaction O((3)P) + HBr → OH + Br, were used to generate functions based on the many-body expansion. The three-body potentials were interpolated using the reproducing kernel Hilbert space method. The resulting surface for the (3)A('') electronic state contains van der Waals minima on the entrance and exit channels and a transition state 6.55 kcal/mol higher than the reactants. This barrier height was then scaled to reproduce the value of 5.01 kcal/mol, which was estimated from coupled cluster benchmark calculations performed to include high-order and core-valence correlation, as well as scalar relativistic effects. The (3)A(') surface was also scaled, based on the fact that in the collinear saddle point geometry these two electronic states are degenerate. The vibrationally adiabatic barrier heights are 3.44 kcal/mol for the (3)A('') and 4.16 kcal/mol for the (3)A(') state.

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI.

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1).

Precisely spun super rotors.

Improved optical control of molecular quantum states promises new applications including chemistry in the quantum regime, precision tests of fundamental physics, and quantum information processing. While much work has sought to prepare ground state molecules, excited states are also of interest. Here, we demonstrate a broadband optical approach to pump trapped SiO+ molecules into pure super rotor ensembles maintained for many minutes. Super rotor ensembles pumped up to rotational state N = 67, corresponding to the peak of a 9400 K distribution, had a narrow N spread comparable to that of a few-kelvin sample, and were used for spectroscopy of the previously unobserved C2Π state. Significant centrifugal distortion of super rotors pumped up to N = 230 allowed probing electronic structure of SiO+ stretched far from its equilibrium bond length.

Treatment of Pediatric Adrenocortical Carcinoma With Surgery, Retroperitoneal Lymph Node Dissection, and Chemotherapy: The Children's Oncology Group ARAR0332 Protocol.

PURPOSE: Adrenocortical carcinoma (ACC) is a rare aggressive pediatric malignancy with distinct biology. Its treatment follows the principles developed for adults; pediatric-specific studies are scarce. PATIENTS AND METHODS: Prospective single-arm risk-stratified interventional study. Study objectives were (1) to describe the outcome of patients with stage I ACC treated with adrenalectomy alone; (2) to describe the outcome of stage II patients (completely resected > 200 cc or > 100 g) treated with adrenalectomy and retroperitoneal lymph node dissection; and (3) to describe the outcome of patients with stage III or IV treated with mitotane and chemotherapy. RESULTS: Between September 2006 and May 2013, 78 patients (77 eligible, 51 females) were enrolled. The 5-year event-free survival estimates for stages I (24 patients), II (15 patients), III (24 patients), and IV (14 patients) were 86.2%, 53.3%, 81%, and 7.1%, respectively. The corresponding 5-year overall survival estimates were 95.2%, 78.8%, 94.7%, and 15.6%, respectively. On univariate analysis, age, stage, presence of virilization, Cushing syndrome, or hypertension, germline TP53 status, and presence of a somatic ATRX mutation were associated with outcome. On multivariable analysis, only stage and age were significantly associated with outcome. The probabilities of mitotane and chemotherapy feasibility events were 10.5% and 31.6%, respectively. CONCLUSION: Outcome for children with stage I ACC is excellent with surgery. Outcome for patients with stage II disease is inferior despite retroperitoneal lymph node dissection. Patients with stage III ACC have an excellent outcome combining surgery and chemotherapy. Patients with stage IV ACC are older and have a poor outcome; new treatments should be explored for this high-risk group. The combination of mitotane and chemotherapy as prescribed in ARAR0332 resulted in significant toxicity; one third of patients with advanced disease could not complete the scheduled treatment.

Computationally Designed 1,2,4-Triazolylidene-Derived N-Heterocyclic Olefins for CO2 Capture, Activation, and Storage.

In this article, triazolylidene-derived N-heterocyclic olefins (trNHOs) are designed using computational quantum tools, and their potential to promote CO2 sequestration is tested and discussed in detail. The low barrier heights related to the trNHO-mediated process indicate that the tailored compounds are very promising for fast CO2 sequestration. The systematic analysis of the presence of distinct substitutes at different N positions of the trNHO ring allows us to rationalize their effect on the carboxylation process and reveal the best N-substituted trNHO systems for CO2 sequestration and improved trNHO carboxylates for faster CO2 capture/release.

How To Arrive at Accurate Benchmark Values for Transition Metal Compounds: Computation or Experiment?

With the objective of analyzing which kind of reference data is appropriate for benchmarking quantum chemical approaches for transition metal compounds, we present the following, (a) a collection of 60 transition metal diatomic molecules for which experimentally derived dissociation energies, equilibrium distances, and harmonic vibrational frequencies are known and (b) a composite computational approach based on coupled-cluster theory with basis set extrapolation, inclusion of core-valence correlation, and corrections for relativistic and multireference effects. The latter correction was obtained from internally contracted multireference coupled-cluster (icMRCC) theory. This composite approach has been used to obtain the dissociation energies and spectroscopic constants for the 60 molecules in our data set. In accordance with previous studies on a subset of molecules, we find that multireference corrections are rather small in many cases and CCSD(T) can provide accurate reference values, if the complete basis set limit is explored. In addition, the multireference correction improves the results in cases where CCSD(T) is not a good approximation. For a few cases, however, strong deviations from experiment persist, which cannot be explained by the remaining error in the computational approach. We suggest that these experimentally derived values require careful revision. This also shows that reliable reference values for benchmarking approximate computational methods are not always easily accessible via experiment and accurate computations may provide an alternative way to access them. In order to assess how the choice of reference data affects benchmark studies, we tested 10 DFT functionals for the molecules in the present data set against experimental and calculated reference values. Despite the differences between these two sets of reference values, we found that the ranking of the relative performance of the DFT functionals is nearly independent of the chosen reference.

Quasiclassical Trajectory Calculations of the Rate Constant of the OH + HBr → Br + H2O Reaction Using a Full-Dimensional Ab Initio Potential Energy Surface Over the Temperature Range 5 to 500 K.

We report a permutationally invariant, ab initio potential energy surface (PES) for the OH + HBr → Br + H2O reaction. The PES is a fit to roughly 26 000 spin-free UCCSD(T)/cc-pVDZ-F12a energies and has no classical barrier to reaction. It is used in quasiclassical trajectory calculations with a focus on the thermal rate constant, k(T), over the temperature range 5 to 500 K. Comparisons with available experimental data over the temperature range 23 to 416 K are made using three approaches to treat the OH rotational and associated electronic partition function. All display an inverse temperature dependence of k(T) below roughly 160 K and a nearly constant temperature dependence above 160 K, in agreement with experiment. The calculated rate constant with no treatment of spin-orbit coupling is overall in the best agreement with experiment, being (probably fortuitously) within 20% of it.

A unique case of synchronous functional adrenocortical adenoma and myelolipoma within the ectopic adrenal cortex in a child with Beckwith-Wiedemann syndrome.

We report a unique case of synchronous functional adrenocortical adenoma and an incidental myelolipoma within ectopic cortical adrenal tissue located in the renal hilum in a child with Beckwith-Wiedemann syndrome and review the association between adrenal gland disorders and myelolipomas. To the best of our knowledge, this is the first documented case of a simultaneous occurrence of these three conditions. A 17-month-old child with Beckwith-Wiedemann syndrome was diagnosed with a left adrenal tumor during complementary radiologic studies. Biochemical investigation before surgery showed elevated blood levels of cortisol and dehydroepiandrosterone hormones. The patient underwent a left adrenalectomy with ipsilateral renal hilar and intercaval-aortic lymph node dissection. Pathology findings revealed a left adrenocortical adenoma and an incidental myelolipoma growing within ectopic cortical adrenal tissue in the renal hilum. The patient is doing well and does not have any current health issues. Patients with adrenal cortex disorders, such as hyperplasias and neoplasms, particularly when associated with hormonal imbalances, may have an increased risk of developing myelolipomas. Whether Beckwith-Wiedemann syndrome may, by itself, contribute to simultaneous occurrence of adrenocortical adenomas and myelolipomas remains to be clarified.