Multireference Ab Initio Calculations on Excited Electronic States of Carbazole-Based Organic Compounds for Thermally Activated Delayed Fluorescence.

The emerging technology of organic light-emitting diodes takes advantage of the thermally activated delayed fluorescence (TADF) mechanism for improved efficiency. Carbazole-based organic molecules are suitable for TADF emission because of charge transfer excitations between the electron-donor carbazole and an electron-acceptor unit. Computational design of new TADF molecules with the desired properties is challenging because charge-transfer excitations cannot be predicted accurately by time-dependent density functional theory.

Spin-orbit coupling in low-lying electronic states of CuH.

Potential energy curves for the low-lying electronic states of CuH have been calculated using the MRCI method with a large active space containing the 3d, 4s, 4p and 3d' orbitals of the copper atom. All electronic states of CuH correlating with the 3d 4s (S) and 3d 4s (D) states of Cu were included, and spin-orbit corrections were calculated using the MRCI wavefunctions. Potential energy curves were obtained for individual states, and the Einstein coefficients were computed for the spin-forbidden transitions from the low-lying electronic states to the XΣ ground state.

How does counter-cation substitution influence inter- and intramolecular hydrogen bonding and electrospinnability of alginates.

Despite numerous applications of nanofibrous alginate (Alg) mat, its facile fabrication via electrospinning is still challenging. The low alginate content compared to the carrier polymer and existence of impurities are the main drawbacks of existing approaches. The purpose of this research is both to study and improve alginate electrospinnability by focusing on the effect of inter- and intramolecular hydrogen bonding.

Ab Initio Calculations on Sequential Reactions of Nitric Oxide with Titanium Ions in the Gas Phase.

Potential energy surfaces of sequential reactions of NO with Ti ion in the gas phase were investigated for various spin multiplicities using the coupled-cluster and the multireference configuration interaction methods. The mechanisms of Ti reactions with up to four NO molecules were fully determined, with all transition-state structures being found by relaxed surface scans and confirmed by the intrinsic reaction coordinate (IRC) calculations. The reaction mechanisms are consistent with the products observed in mass spectrometric experiments.

Determination of ν2 fundamental band origin for BeH2 and BeD2 from deperturbation analysis of hot bands.

New vibration-rotation hot bands, i.e., 031 → 030 and 041 → 040, have been assigned and rotationally analyzed for the gaseous BeH2 molecule.

A Simple Colorimetric Chemosensor for Naked Eye Detection of Cyanide Ion.

A simple cyanide chemosensor tetranitrile compound 1 was designed and synthesized via an efficient method in the presence of nanoporous SBA-Pr-NH2 as the catalyst. The chemosensor exhibited high selectivity and sensitivity for detecting CN¯ among different anions through a visual color change from light yellow to purple. The results confirmed that the chemosensor 1 causes the color of the solution to change depending on the concentration of CN¯.

Structural stability of myoglobin and glycomyoglobin: a comparative molecular dynamics simulation study.

Glycoproteins are formed as the result of enzymatic glycosylation or chemical glycation in the body, and produced in vitro in industrial processes. The covalently attached carbohydrate molecule(s) confer new properties to the protein, including modified stability. In the present study, the structural stability of a glycoprotein form of myoglobin, bearing a glucose unit in the N-terminus, has been compared with its native form by the use of molecular dynamics simulation.

Potential energy curves for the ground and low-lying excited states of CuAg.

The ground and low-lying excited states of heteronuclear diatomic CuAg are examined by multi-reference configuration interaction (MRCI) method. Relativistic effects were treated and probed in two steps. Scalar terms were considered using the spin-free DKH Hamiltonian as a priori and spin-orbit coupling was calculated perturbatively via the spin-orbit terms of the Breit-Pauli Hamiltonian based on MRCI wavefunctions.

Accurate analytic potential and Born-Oppenheimer breakdown functions for MgH and MgD from a direct-potential-fit data analysis.

New high-resolution visible Fourier transform emission spectra of the A (2)Π → X (2)Σ(+) and B' (2)Σ(+) → X (2)Σ(+) systems of (24)MgD and of the B' (2)Σ(+) → X (2)Σ(+) systems of (25,26)MgD and (25,26)MgH have been combined with earlier results for (24)MgH in a multi-isotopologue direct-potential-fit analysis to yield improved analytic potential energy and Born-Oppenheimer breakdown functions for the ground X (2)Σ(+) state of MgH. Vibrational levels of the ground state of (24)MgD were observed up to v" = 15, which is bound by only 30.6 ± 0.

Spin-orbit and relativistic all-electron potential energy curves for the ground and low-lying excited states of AgAu.

The spin-free and spin-orbit potential energy curves of ground and excited states of AgAu up to 5 eV have been investigated. Calculations have been performed at the all-electron level with scalar relativistic effects included through the second-order Douglas-Kroll-Hess Hamiltonian. We have used the complete active space multi-configuration self-consistent field method, followed by the multi-reference configuration interaction (MRCI) calculations.

Rotational analysis and deperturbation of the A2Π → X2Σ+ and B'2Σ+ → X2Σ+ emission spectra of MgH.

Deperturbation analysis of the A(2)Π → X(2)Σ(+) and B(')(2)Σ(+) → X(2)Σ(+) emission spectra of (24)MgH is reported. Spectroscopic data for the v = 0 to 3 levels of the A (2)Π state and the v = 0 to 4 levels of the B'(2)Σ(+) state were fitted together using a single Hamiltonian matrix that includes (2)Π and (2)Σ(+) matrix elements, as well as off-diagonal elements coupling several vibrational levels of the two states. A Dunham-type fit was performed and the resulting Y(l,0) and Y(l,1) coefficients were used to generate Rydberg-Klein-Rees (RKR) potential curves for the A (2)Π and the B'(2)Σ(+) states.

Note: Deperturbation of the ν3 band of BeD2.

High rotational levels of the 001 (Σ(u)) state of BeD(2) are perturbed by the nearby 03(3)0 (Φ(u)) state. Deperturbation analysis results in an experimental value for the vibrational energy of the 030 level.

Reactions of atomic cations with methane: gas phase room-temperature kinetics and periodicities in reactivity.

Reactions of methane have been measured with 59 atomic metal cations at room temperature in helium bath gas at 0.35 Torr using an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. The atomic cations were produced at approximately 5500 K in an ICP source and allowed to decay radiatively and to thermalize by collisions with argon and helium atoms prior to reaction.

Gas-phase reactions of sulfur hexafluoride with transition metal and main group atomic cations: room-temperature kinetics and periodicities in reactivity.

Gas-phase reactions of SF(6) were investigated with 46 different atomic metal and main group cations at room temperature using an Inductively-Coupled Plasma/Selected-Ion Flow Tube (ICP/SIFT) tandem mass spectrometer. The atomic ions were produced at about 5500 K in the ICP source and allowed to decay radiatively and to thermalize by collisions with argon and helium atoms prior to reaction downstream in a flow tube in helium buffer gas at 0.35 +/- 0.

Ground state potential energy curve and dissociation energy of MgH.

New high-resolution visible emission spectra of the MgH molecule have been recorded with high signal-to-noise ratios using a Fourier transform spectrometer. Many bands of the A 2Pi-->X 2Sigma+ and B' 2Sigma+-->X 2Sigma+ electronic transitions of 24MgH were analyzed; the new data span the v' = 0-3 levels of the A 2Pi and B'2Sigma+ excited states and the v''=0-11 levels of the X 2Sigma+ ground electronic state. The vibration-rotation energy levels of the perturbed A 2Pi and B' 2Sigma+ states were fitted as individual term values, while those of the X 2Sigma+ ground state were fitted using the direct-potential-fit approach.

The vibration-rotation emission spectrum of gaseous HZnCl.

Gaseous HZnCl has been synthesized for the first time in a high-temperature tube furnace with a dc discharge in a flowing mixture of pure HCl and Zn vapor. The vibration-rotation emission spectrum of HZnCl was recorded at high resolution using a Fourier transform spectrometer. The H-Zn stretching modes (nu(1)) of the H(64)Zn(35)Cl, H(66)Zn(35)Cl, H(68)Zn(35)Cl, and H(64)Zn(37)Cl species, as well as the 2nu(1)-nu(1) hot band of the most abundant isotopologue H(64)Zn(35)Cl, were observed near 1966 cm(-1).

Infrared emission spectra and equilibrium structures of gaseous HgH2 and HgD2.

A detailed analysis of the high-resolution infrared emission spectra of gaseous HgH2 and HgD2 in the 1200-2200 cm(-1) spectral range is presented. The nu3 antisymmetric stretching fundamental bands of 204HgH2, 202HgH2, 201HgH2, 200HgH2, 199HgH2, 198HgH2, 204HgD2, 202HgD2, 201HgD2, 200HgD2, 199HgD2, and 198HgD2, as well as a few hot bands involving nu1, nu2, and nu3 were analyzed rotationally, and spectroscopic constants were obtained. Using the rotational constants of the 000, 100, 01(1)0, and 001 vibrational levels, we determined the equilibrium rotational constants (B(e)) of the most abundant isotopologues, 202HgH2 and 202HgD2, to be 3.

Direct-potential-fit analysis of new infrared and UV/visible A 1Sigma+-X 1Sigma+ emission spectra of AgH and AgD.

New high-resolution infrared and UV/visible spectra of (107)AgH, (109)AgH, (107)AgD, and (109)AgD have been recorded with a Fourier transform spectrometer. The new line positions are combined with published microwave and older electronic A (1)Sigma(+)-X (1)Sigma(+) data and used, first in a decoupled analysis of the X state alone, and then in a global multi-isotopologue analysis which yields comprehensive descriptions of both the X (1)Sigma(+) and A (1)Sigma(+) states of all four isotopologues of AgH. While the A state was long believed to be heavily perturbed, it is shown that its irregular spectrum merely reflects an unusual potential function shape.

Infrared emission spectra and equilibrium bond lengths of gaseous ZnH2 and ZnD2.

A detailed analysis of the high resolution infrared emission spectra of gaseous ZnH2 and ZnD2 in the 800-2200 cm(-1) spectral range is presented. The nu3 antisymmetric stretching fundamental bands of 64ZnH2, 66ZnH2, 67ZnH2, 68ZnH2, 64ZnD2, 66ZnD2 and 68ZnD2, as well as several hot bands involving nu1, nu2 and nu3 were rotationally analyzed, and spectroscopic constants were obtained. Rotational l-type doubling and l-type resonance, local perturbations, and Fermi resonances were observed in the vibration-rotation bands of both ZnH2 and ZnD2, and equilibrium vibrational frequencies (omega1, omega2 and omega3) were estimated.

The vibration-rotation emission spectrum of hot BeF2.

The high-resolution infrared emission spectrum of BeF2 vapor at 1000 degrees C was rotationally analyzed with the assistance of large-scale ab initio calculations using the coupled-cluster method including single and double excitations and perturbative inclusion of triple excitations, in conjunction with correlation-consistent basis sets up to quintuple-zeta quality. The nu3 fundamental band, the nu1+nu2, nu1+nu3, and 2nu2+nu3 combination bands, and 18 hot bands were assigned. The symmetric stretching (nu1), bending (nu2), and antisymmetric stretching (nu3) mode frequencies were determined to be 769.

The vibration-rotation emission spectra of gaseous CdH2 and CdD2.

The vibration-rotation emission spectra of CdH2 and CdD2 molecules have been recorded at high resolution using a Fourier-transform spectrometer. The molecules were generated in a furnace-discharge emission source by reaction of cadmium vapor with molecular hydrogen or deuterium. The fundamental bands for the antisymmetric stretching mode (upsilon3) of CdH2 and CdD2 were detected at about 1771.

Gaseous HgH2, CdH2, and ZnH2.

Gaseous HgH2, CdH2, and ZnH2 molecules were synthesized by the direct gas-phase reaction of excited mercury, cadmium, and zinc atoms with molecular hydrogen. The molecules were identified by their high-resolution infrared emission spectra, and the metal-hydrogen bond lengths were determined from the rotational analysis of the antisymmetric stretching fundamental bands.

Vibration-rotation emission spectra of gaseous ZnH2 and ZnD2.

Gaseous ZnH2 and ZnD2 have been discovered in an emission source that combines an electrical discharge with a high-temperature furnace. High-resolution infrared emission spectra of ZnH2 and ZnD2 have been recorded with a Fourier transform spectrometer, and the antisymmetric stretching fundamental bands of 64ZnH2 and 64ZnD2 were detected near 1889.4 and 1371.

The vibration-rotation emission spectrum of free BeH2.

The gaseous BeH2 molecule has been synthesized by means of an electrical discharge inside a high-temperature furnace and identified with infrared emission spectroscopy. The antisymmetric stretching mode nu3 has been detected near 2179 reciprocal centimeters. The BeH2 molecule has a linear, symmetric structure with an r0 BeH bond length of 1.