Papillary urothelial neoplasm of low malignant potential with osseous metaplasia in a 19-year-old chronic smoker: A case report with review of literature.

Urothelial tumors characteristically occur in elderly persons, more commonly in males with typical complaints of hematuria. Although few studies attempted to describe clinic-pathological features of urothelial malignancies in young patients, due to heterogeneity in the inclusion of age groups under "young patients" no reliable conclusions can be derived. Herein, we are describing an interesting case of papillary urothelial neoplasm of low malignant potential with osseous metaplasia in a 19-year-old chronic smoker young patient presented with chief complaints of abdominal pain with a review of the literature.

PPP2R5D-Related Neurodevelopmental Disorder or Developmental and Epileptic Encephalopathy?: A Novel Phenotypic Description and Review of Published Cases.

BACKGROUND: Protein phosphatase 2 regulatory subunit B' delta (PPP2R5D)-related neurodevelopmental disorder is caused by pathogenic variations in the PPP2R5D gene, product of which is involved in dephosphorylation. This is a rare disorder with description limited to case reports. Its phenotypic spectrum has expanded over the last decade. METHODS: We report a child with a developmental and epileptic encephalopathy phenotype with a pathogenic PPP2R5D variant. This phenotype has not been previously reported. We also reviewed the previously published reports of patients with this disorder. RESULTS: Including the index child, 28 cases (15 girls) were identified from nine relevant research items for analysis. All patients had developmental delay. History of seizures was observed in seven patients while macrocephaly was seen in nearly 80% of patients. Nonneurological manifestations were observed in 13 patients with the most common one being ophthalmological manifestations. The most common genetic variation was c.G592A (p.E198K). The common phenotypic associations of this variation were developmental delay, macrocephaly (11/15), and epilepsy (6/15). CONCLUSION: PPP2R5D gene variations should be suspected in children with developmental delay, autistic features, macrocephaly with or without epilepsy in the absence of any clear etiology. Dysmorphic features might provide a diagnostic clue. DEE phenotype may also be the presenting feature and might be an underreported entity.

Interatomic potentials for ground and excited states of Ar+He.

The potential energy curves (PECs) of the ground and excited states that correlate in the atomic limit with Ar([Ne]3s 23p 6,1S), Ar([Ne]3s 23p 54s 1, 3P, 1P), and Ar([Ne]3s 23p 54p 1, 3D, 3P, 3S, 1D, 1P, 1S) are calculated at the multireference configuration interaction (MRCI+Q) theoretical level with extrapolations to the complete basis set limit using all-electron correlation consistent triple-, quadruple-, and quintuple-zeta basis sets. Scalar relativistic corrections are calculated using second-order Douglas-Kroll-Hess Hamiltonian with the corresponding basis sets contracted for scalar relativistic Hamiltonians. For these calculations, the 3s orbitals of the Ar atom are not included in the active space but are correlated through single and double excitations. Spin-orbit eigenstates are computed by diagonalizing the Breit-Pauli matrix between internal configurations with no electrons in external orbitals and added to the scalar relativistic results. A total of 32 molecular PECs are computed with spin-orbit contributions, which correlate with 1s1, 1s5-2, and 2p10-1 atomic Ar energies in Paschen notation. Important features of the PECs and system crossings are discussed.

Excited interatomic potential energy surfaces of Rb + He that correlate with Rb terms 52S through 72S.

The excited state interatomic potential energy surfaces for Rb + He are computed at the spin-orbit multi-reference configuration interaction level of theory using all-electron basis sets of triple and quadruple-zeta quality that have been contracted for Douglas-Kroll-Hess (DKH) Hamiltonian and includes core-valence correlation. Davidson-Silver corrections (MRCI+Q) are employed to ameliorate size consistency error. An extrapolation of CASSCF energies is performed using the procedure of Karton and Martin whereas extrapolation of correlation energy is performed using an expression involving the inverse powers of (lmax + 1/2), the highest angular momentum value present in the basis set. The spin-orbit energies in the limit of complete basis set are obtained by replacing the energy eigenvalues in the spin-orbit matrix by the relativistic-corrected MRCI+Q energies extrapolated to the complete basis set limit. MRCI diabatic potential energy surfaces for a few selected 2Σ states are calculated to study the general topology and avoided crossings and repulsive form of the 6s 2Σ+ state. Important features of the potential energy surfaces are discussed with implications for alkali laser spectroscopy.

Chemical activation through super energy transfer collisions.

Can a molecule be efficiently activated with a large amount of energy in a single collision with a fast atom? If so, this type of collision will greatly affect molecular reactivity and equilibrium in systems where abundant hot atoms exist. Conventional expectation of molecular energy transfer (ET) is that the probability decreases exponentially with the amount of energy transferred, hence the probability of what we label "super energy transfer" is negligible. We show, however, that in collisions between an atom and a molecule for which chemical reactions may occur, such as those between a translationally hot H atom and an ambient acetylene (HCCH) or sulfur dioxide, ET of chemically significant amounts of energy commences with surprisingly high efficiency through chemical complex formation. Time-resolved infrared emission observations are supported by quasi-classical trajectory calculations on a global ab initio potential energy surface. Results show that ∼10% of collisions between H atoms moving with ∼60 kcal/mol energy and HCCH result in transfer of up to 70% of this energy to activate internal degrees of freedom.

First-principles calculations of rovibrational energies, dipole transition intensities and partition function for ethylene using MULTIMODE.

Large-scale, rovibrational variational calculations are performed for ethylene, using the potential energy surface published by Avila and Carrington [J. Chem. Phys. 135, 064101 (2011)]. Energies for J = 0 are in very good agreement with their benchmark results. Corresponding energies for J = 1 and J = 2 are also given. Calculations with a slightly reduced basis permit energies to J = 40, allowing a reliable determination of the partition function at 296 K. Using a new ab initio dipole moment surface, reported here, the infrared spectra of five dipole-allowed fundamentals are calculated. Both the partition function and infrared spectra are shown to be in excellent agreement with those in the experimental HITRAN database, with the exception of one band, which we believe is partially mis-assigned in HITRAN.

Quasiclassical trajectory study of fast H-atom collisions with acetylene.

Translationally hot H collisions with the acetylene are investigated using quasiclassical trajectory calculations, on a recent full-dimensional ab initio-based potential energy surface. Three outcomes are focused on: non-reactive energy transfer via prompt collisions, non-reactive energy transfer via the formation of the vinyl complex, and reactive chemical H-atom exchange, also via complex formation. The details of these outcomes are presented and correlated with the collision lifetime. Large energy transfer is found via complex formation, which can subsequently decay back to reactants, a non-reactive event, or to new products, a reactive event. For the present system, these two events are experimentally indistinguishable.

Large-amplitude dynamics in vinyl radical: the role of quantum tunneling as an isomerization mechanism.

We report tunneling splittings associated with the large amplitude 1,2 H-atom migration to the global minima in the vinyl radical. These are obtained using a recent full-dimensional ab initio potential energy surface (PES) [A. R. Sharma, B. J. Braams, S. Carter, B. C. Shepler, and J. M. Bowman, J. Chem. Phys. 130(17), 174301 (2009)] and independently, directly calculated "reaction paths." The PES is a multidimensional fit to coupled cluster single and double and perturbative treatment of triple excitations coupled-cluster single double triple (CCSD(T)) with the augmented correlation consistent triple zeta basis set (aug-cc-pVTZ). The reaction path potentials are obtained from a series of CCSD(T)/aug-cc-pVnTZ calculations extrapolated to the complete basis set limit. Approximate 1D calculations of the tunneling splitting for these 1,2-H atom migrations are obtained using each of these potentials as well as quite different 1D Hamiltonians. The splittings are calculated over a large energy ranges, with results from the two sets of calculations in excellent agreement. Though negligibly slow (>1 s) for the vibrational ground state, this work predicts tunneling-promoted 1,2 hydride shift dynamics in vinyl to exhibit exponential growth with internal vibrational excitation, specifically achieving rates on the sub-µs time scale at energies above E ≈ 7500 cm(-1). Most importantly, these results begin to elucidate the possible role of quantum isomerization through barriers without dissociation, in competition with the more conventional picture of classical roaming permitted over a much narrower window of energies immediately below the bond dissociation limit. Furthermore, when integrated over a Boltzmann distribution of thermal energies, these microcanonical tunneling rates are consistent with sub-µs time scales for 1,2 hydride shift dynamics at T > 1400 K. These results have potential relevance for combustion modeling of low-pressure flames, as well as recent observations of nuclear spin statistical mixing from high-resolution IR/microwave spectroscopy on vinyl radical.

Multimode calculations of rovibrational energies and dipole transition intensities for polyatomic molecules with torsional motion: application to H2O2.

We report rigorous calculations of rovibrational energies and dipole transition intensities for hydrogen peroxide using a new version of MULTIMODE as applied to molecules with torsional (reaction path) motion. The key features which permit such calculations for moderately sized polyatomic molecules of this general type are briefly described. A previous, accurate potential energy surface and a new high-level ab initio dipole moment surface are employed in these calculations. Detailed comparisons are made with high-resolution experimental spectral intensities from the HITRAN database.

Calculations of rovibrational energies and dipole transition intensities for polyatomic molecules using MULTIMODE.

We report rigorous calculations of rovibrational energies and dipole transition intensities for three molecules using a new version of the code MULTIMODE. The key features of this code which permit, for the first time, such calculations for moderately sized but otherwise general polyatomic molecules are briefly described. Calculations for the triatomic molecule BF(2) are done to validate the code. New calculations for H(2)CO and H(2)CS are reported; these make use of semiempirical potentials but ab initio dipole moment surfaces. The new dipole surface for H(2)CO is a full-dimensional fit to the dipole moment obtained with the coupled-cluster with single and double excitations and a perturbative treatment of triple excitations method with the augmented correlation consistent triple zeta basis set. Detailed comparisons are made with experimental results from a fit to relative data for H(2)CS and absolute intensities from the HITRAN database for H(2)CO.

Full-dimensional ab initio potential energy surface and vibrational configuration interaction calculations for vinyl.

The potential energy landscape and two permutationally invariant, full-dimensional ab initio-based potential energy surfaces (PESs) for the doublet vinyl radical, C(2)H(3), are described. The first of the two surfaces, denoted as PES/S, describes the equivalent CH(2)CH global minimum and the saddle point separating them, planar and nonplanar H-atom migration saddle points, a methylcarbyne local minimum that is due to a Jahn-Teller conical intersection, and the saddle point connecting it with the global minimum. The second PES, denoted PES/D, contains all stationary points of PES/S and in addition describes dissociation to C(2)H(2)+H fragments, including the saddle point to dissociation along a least-energy path. The surfaces are least-squares fits to electronic energies obtained with use of the spin-restricted coupled cluster singles and doubles with perturbative treatment of triples method and augmented correlation consistent polarized valence triple zeta basis sets, using permutationally invariant polynomials in "Morse variables" and a many-body expansion. PES/S is a fit to roughly 34,000 and PES/D to roughly 50,000 electronic structure energies. PES/S is used in full-dimensional, vibrational configuration interaction calculations of the vinyl zero-point energy and fundamental vibrational energies, which are compared to recent experiments.

Potential energy surface and MULTIMODE vibrational analysis of C2H3+.

A full dimensional, ab initio-based semiglobal potential energy surface for C(2)H(3) (+) is reported. The ab initio electronic energies for this molecule are calculated using the spin-restricted, coupled cluster method restricted to single and double excitations with triples corrections [RCCSD(T)]. The RCCSD(T) method is used with the correlation-consistent polarized valence triple-zeta basis augmented with diffuse functions (aug-cc-pVTZ). The ab initio potential energy surface is represented by a many-body (cluster) expansion, each term of which uses functions that are fully invariant under permutations of like nuclei. The fitted potential energy surface is validated by comparing normal mode frequencies at the global minimum and secondary minimum with previous and new direct ab initio frequencies. The potential surface is used in vibrational analysis using the "single-reference" and "reaction-path" versions of the code MULTIMODE.