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##### The pure rotational spectrum of the ZnBr radical (X2Σ+): Trends in the zinc halide series

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

The pure rotational spectrum of ZnBr (X2Σ+) has been recorded in the frequency range 259-310 GHz using millimeter-wave direct absorption techniques. This study is the first quantitative spectroscopic investigation of this free radical. ZnBr was synthesized in a DC discharge by the reaction of zinc vapor in argon with one of three reagents: BrCH3, Br2CH2, or Br2. Eight rotational transitions were measured for six isotopologues (64Zn79Br, 64Zn81Br, 66Zn79Br, 66Zn81Br, 68Zn79Br, and 68Zn81Br), all of which exhibited spin-rotation interactions. Furthermore, transitions originating in the v = 1 through 3 excited vibrational states were obtained for certain isotopologues. Five rotational transitions were also recorded for 67Zn79Br, in which hyperfine splittings were observed arising from the 67Zn nucleus (I = 5/2). The spectra were analyzed using a Hund’s case (bβJ) Hamiltonian, and rotational, spin-rotation, and 67Zn magnetic hyperfine constants were determined. Equilibrium parameters were also derived for the 64Zn79Br, 64Zn81Br, 66Zn79Br, and 66Zn81Br isotopologues, including the vibrational constant, ωe = 286 cm-1. The equilibrium bond length was derived to be re = 2.268 48(90) Å. Analysis of the 67Zn hyperfine parameters suggest a decrease in ionic character in ZnBr from the other known zinc halides, ZnF and ZnCl.

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##### Penning collisions between supersonically expanded metastable He atoms and laser-cooled Li atoms

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

We describe an experimental setup comprised of a discharge source for supersonic beams of metastable He atoms and a magneto-optical trap (MOT) for ultracold Li atoms that makes it possible to study Penning ionization and associative ionization processes at high ion count rates. The cationic reaction products are analyzed using a novel ion detection scheme which allows for mass selection, a high ion extraction efficiency, and a good collision-energy resolution. The influence of elastic He-Li collisions on the steady-state Li atom number in the MOT is described, and the collision data are used to estimate the excitation efficiency of the discharge source. We also show that Penning collisions can be directly used to probe the temperature of the Li cloud without the need for an additional time-resolved absorption or fluorescence detection system.

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##### Prediction of many-electron wavefunctions using atomic potentials: Refinements and extensions to transition metals and large systems

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

For a given many-electron molecule, it is possible to define a corresponding one-electron Schrödinger equation, using potentials derived from simple atomic densities, whose solution predicts fairly accurate molecular orbitals for single-determinant and multideterminant wavefunctions for the molecule. The energy is not predicted and must be evaluated by calculating Coulomb and exchange interactions over the predicted orbitals. Transferable potentials for first-row atoms and transition metal oxides that can be used without modification in different molecules are reported. For improved accuracy, molecular wavefunctions can be refined by slightly scaling nuclear charges and by introducing potentials optimized for functional groups. The accuracy is further improved by a single diagonalization of the Fock matrix constructed from the predicted orbitals. For a test set of 20 molecules representing different bonding environments, the transferable potentials with scaling give wavefunctions with energies that deviate from exact self-consistent field or configuration interaction energies by less than 0.05 eV and 0.02 eV per bond or valence electron pair, respectively. On diagonalization of the Fock matrix, the corresponding errors are reduced by a factor of three to less than 0.016 eV and 0.006 eV, respectively. Applications to the ground and excited states of a Ti18O36 nanoparticle and chlorophyll-a are reported.

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##### Direct evaluation of the force constant matrix in quantum Monte Carlo

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

We develop a formalism to directly evaluate the matrix of force constants within a Quantum Monte Carlo calculation. We utilize the matrix of force constants to accurately relax the positions of atoms in molecules and determine their vibrational modes, using a combination of variational and diffusion Monte Carlo. The computed bond lengths differ by less than 0.007 Å from the experimental results for all four tested molecules. For hydrogen and hydrogen chloride, we obtain fundamental vibrational frequencies within 0.1% of experimental results and ∼10 times more accurate than leading computational methods. For carbon dioxide and methane, the vibrational frequency obtained is on average within 1.1% of the experimental result, which is at least 3 times closer than results using restricted Hartree-Fock and density functional theory with a Perdew-Burke-Ernzerhof functional and comparable or better than density functional theory with a semi-empirical functional.

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##### Water structure at the interface of alcohol monolayers as determined by molecular dynamics simulations and computational vibrational sum-frequency generation spectroscopy

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

We investigate the structure of water at the interface of three long-chain alcohol monolayers differing in alkyl chain length through molecular dynamics simulations combined with modeling of vibrational sum-frequency generation (vSFG) spectra. The effects of alkyl chain parity on interfacial water are examined through extensive analysis of structural properties, hydrogen bonding motifs, and spectral features. Besides providing molecular-level insights into the structure of interfacial water, this study also demonstrates that, by enabling comparisons with experimental vSFG spectra, computational spectroscopy may be used to test and validate force fields commonly used in biomolecular simulations. The results presented here may serve as benchmarks for further investigations to characterize ice nucleation induced by alcohol monolayers.

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##### Application of the Cauchy integral formula as a tool of analytic continuation for the resummation of divergent perturbation series

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

Previous attempts to the resummation of divergent power series by means of analytic continuation are improved applying the Cauchy integral formula for complex functions. The idea is tested on divergent Møller-Plesset perturbation expansions of the electron correlation energy. In particular, the potential curve of the LiH molecule is computed from single reference MPn results which are divergent for bond distances larger than 3.6 Å. Preliminary results for the Hartree-Fock molecule are also tabulated.

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##### Cluster expansion based configurational averaging approach to bandgaps of semiconductor alloys

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

Configurationally disordered semiconducting materials including semiconductor alloys [e.g., (GaN)1-x(ZnO)x] and stoichiometric materials with fractional occupation (e.g., LaTiO2N) have attracted a lot of interest recently in search for efficient visible light photo-catalysts. First-principles modeling of such materials poses great challenges due to the difficulty in treating the configurational disorder efficiently. In this work, a configurational averaging approach based on the cluster expansion technique has been exploited to describe bandgaps of ordered, partially disordered (with short-range order), and fully disordered phases of semiconductor alloys on the same footing. We take three semiconductor alloys [Cd1-xZnxS, ZnO1-xSx, and (GaN)1-x(ZnO)x] as model systems and clearly demonstrate that semiconductor alloys can have a system-dependent short-range order that has significant effects on their electronic properties.

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##### Selective photoisomerisation of 2-chloromalonaldehyde

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

Isomerization of 2-chloromalonaldehyde (2-ClMA) is explored giving access to new experimental data on this derivative of malonaldehyde, not yet studied much. Experiments were performed isolating 2-ClMA in argon, neon, and para-hydrogen matrices. UV irradiation of the matrix samples induced isomerization to three open enolic forms including two previously observed along with the closed enolic form after deposition. IR spectra of these specific conformers were recorded, and a clear assignment of the observed bands was obtained with the assistance of theoretical calculations. UV spectra of the samples were measured, showing a blue shift of the π* ← π absorption with the opening of the internal hydrogen bond of the most stable enol form. Specific sequences of UV irradiation at different wavelengths allowed us to obtain samples containing only one enol conformer. The formation of conformers is discussed. The observed selectivity of the process among the enol forms is analyzed.

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##### Influence of non-Markovian dynamics in equilibrium uncertainty-relations

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

Contrary to the conventional wisdom that deviations from standard thermodynamics originate from the strong coupling to the bath, it is shown that in quantum mechanics, these deviations originate from the uncertainty principle and are supported by the non-Markovian character of the dynamics. Specifically, it is shown that the lower bound of the dispersion of the total energy of the system, imposed by the uncertainty principle, is dominated by the bath power spectrum; therefore, quantum mechanics inhibits the system thermal-equilibrium-state from being described by the canonical Boltzmann’s distribution. We show for a wide class of systems, systems interacting via central forces with pairwise-self-interacting environments; this general observation is in sharp contrast to the classical case, for which the thermal equilibrium distribution, irrespective of the interaction strength, is exactly characterized by the canonical Boltzmann distribution; therefore, no dependence on the bath power spectrum is present. We define an effective coupling to the environment that depends on all energy scales in the system and reservoir interaction. Sample computations in regimes predicted by this effective coupling are demonstrated. For example, for the case of strong effective coupling, deviations from standard thermodynamics are present and for the case of weak effective coupling, quantum features such as stationary entanglement are possible at high temperatures.

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##### A classical ride through a conical intersection

- The Journal of chemical physics
- Published about 15 hours ago
- Discuss

Regarding the correlated electron-nuclear motion in a model system, we investigate the dynamics in the vicinity of a conical intersection (CoIn) between two excited state potential surfaces. It is documented that an ensemble of classical trajectories which move in the complete electronic-nuclear phase space tracks the quantum wave-packet motion through the CoIn which is accompanied by a non-adiabatic population transfer. On the contrary, for an adiabatic circular motion around the position of the CoIn, the quantum mechanical and classical densities deviate substantially. In the latter case, the Born-Oppenheimer classical nuclear motion on a single potential surface is able to track the quantum dynamics.