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We investigate the vibrational shift of beryllium oxide (BeO) in Xe matrix as well as in Ar matrix environments by mixed quantum-classical simulation and examine the origin of spectral shift in details. BeO is known to form strong chemical complex with single rare gas atom, and it is predicted from the gas phase calculations that vibrational frequencies are blueshifted by 78 cm^[-1] and 80 cm^[-1] upon formation of XeBeO and ArBeO, respectively. When the effects of other surrounding rare gas atoms are included by Monte Carlo simulations, it is found that the vibrational frequencies are redshifted by 21 cm^[-1] and 8 cm^[-1] from the isolated XeBeO and ArBeO complexes, respectively. The vibrational shift of XeBeO in Ar matrix is also calculated and compared with experimental data. In all simulations examined in this paper, the calculated vibrational frequency shifts from the isolated BeO molecule are in reasonable agreement with experimental values. The spectral shift due to the rare-gas-complex formation of RgBeO (Rg = Xe or Ar) is not negligible as seen in the previous studies, but it is shown in this paper that the effects of other surrounding rare gas atoms should be carefully taken into account for quantitative description of the spectral shifts and that these two effects are competing in vibrational spectroscopy of BeO in matrix environments.

The ultrafast electronic dynamics of pyrazine (C4N2H4) were studied by time-resolved photoelectron imaging (TRPEI) using the third (3ω, 4.7 eV) and fifth harmonics (5ω, 7.8 eV) of a femtosecond Ti:sapphire laser (ω). Although the photoionization signals due to the 5ω - 3ω and 3ω - 5ω pulse sequences overlapped near the time origin, we have successfully extracted their individual TRPEI signals using least squares fitting of the observed electron kinetic energy distributions. When the 5ω pulses preceded the 3ω pulses, the 5ω pulses predominantly excited the S4 (ππ∗, 1B1 u+1B2u) state. The photoionization signal from the S4 state generated by the time-delayed 3ω pulses was dominated by the D3(2B2g)←S4 photoionization process and exhibited a broad electron kinetic energy distribution, which rapidly downshifted in energy within 100 fs. Also observed were the photoionization signals for the 3s, 3pz, and 3py members of the Rydberg series converging to D0(2Ag). The Rydberg signals appeared immediately within our instrumental time resolution of 27 fs, indicating that these states are directly photoexcited from the ground state or populated from S4 within 27 fs. The 3s, 3pz, and 3py states exhibited single exponential decay with lifetimes of 94 ± 2, 89 ± 2, and 58 ± 1 fs, respectively. With the reverse pulse sequence of 3ω - 5ω, the ultrafast internal conversion (IC) from S2(ππ∗) to S1(nπ∗) was observed. The decay associated spectrum of S2 exhibited multiple bands ascribed to D0, D1, and D3, in agreement with the 3ω-pump and 6ω-probe experiment described in our preceding paper [T. Horio et al., J. Chem. Phys. 145, 044306 (2016)]. The electron kinetic energy and angular distributions from S1 populated by IC from S2 are also discussed.

In the present study, variational path integral molecular dynamics and associated hybrid Monte Carlo (HMC) methods have been developed on the basis of a fourth order approximation of a density operator. To reveal various parameter dependence of physical quantities, we analytically solve one dimensional harmonic oscillators by the variational path integral; as a byproduct, we obtain the analytical expression of the discretized density matrix using the fourth order approximation for the oscillators. Then, we apply our methods to realistic systems like a water molecule and a para-hydrogen cluster. In the HMC, we adopt two level description to avoid the time consuming Hessian evaluation. For the systems examined in this paper, the HMC method is found to be about three times more efficient than the molecular dynamics method if appropriate HMC parameters are adopted; the advantage of the HMC method is suggested to be more evident for systems described by many body interaction. © 2016 Author(s)., after 12 months embargo

In this paper, a full account of an earlier report [Takahashi, Okuyama, and Kimura, J. Mol. Struct. 249, 47 (1991)] on the cation vibrational spectra of trans and gauche n‐propylbenzene, which were obtained by means of a two‐color (1+1’) multiphoton ionization threshold photoelectron technique is presented. The trans and gauche cations were separately produced by (1+1’) multiphoton ionization resonant through the S1 vibronic levels of n‐propylbenzene in supersonic free jets in which both the trans and gauche isomers exist. From the observed threshold photoelectron spectra, adiabatic ionization energies are determined as Ia(trans)=70 278 cm−1 (8.7134 eV) and Ia(gauche)=70 420 cm−1 (8.7311 eV) with an accuracy of ±8 cm−1 (±1 meV). Furthermore, four benzene ring modes (6b+, 1+, 12+, and 18a+) as well as several low‐frequency torsional and bending modes have been identified which are sensitive to the relative conformations of the n‐propyl group with respect to the benzene ring [(trans)+: 82, 212, and 300 cm−1...

This paper discusses the conformational phase change of an isolated polymer chain which is capable of forming physical bonds with solvent molecules. On the basis of the mean‐field theory of Flory type, we derive a formula for the temperature dependence of the expansion factor of the chain. Our theory takes account of the extra mixing entropy change induced by the solvation. We predict that the physical‐bond formation between polymer and solvent molecules causes a reentrant conformational change between coiled and globular state when temperature is varied. We also show that the polymer chain exhibits a sharp collapse near the Θ temperature as the temperature is increased to the lower critical solution temperature of the polymer solution. This behavior can be interpreted in terms of the breakup of the polymer–solvents complex. The result is compared with the observed coil–globule transition on poly (N‐isopropylacrylalmide) in water.

The hydrogen storage system LiH + NH(3) ↔ LiNH(2) + H(2) is one of the most promising hydrogen storage systems, where the reaction yield can be increased by replacing Li in LiH with other alkali metals (Na or K) in order of LiNaK. In this paper, we have studied the alkali metal M (M = Li, Na, K) dependence of the reactivity of MH with NH(3) by calculating the potential barrier of the H(2) desorption process from the reaction of an M(2)H(2) cluster with an NH(3) molecule based on the ab initio structure optimization method. We have shown that the height of the potential barrier becomes lower in order of Li, Na, and K, where the difference of the potential barrier in Li and Na is relatively smaller than that in Na and K, and this tendency is consistent with the recent experimental results. We have also shown that the H-H distance of the H(2) dimer at the transition state takes larger distance and the change of the potential energy around the transition state becomes softer in order of Li, Na, and K. There are almost no M dependence in the charge of the H atom in NH(3) before the reaction, while that of the H atom in M(2)H(2) takes larger negative value in order of Li, Na, and K. We have also performed molecular dynamics simulations on the M(2)H(2)-NH(3) system and succeeded to reproduce the H(2) desorption from the reaction of Na(2)H(2) with NH(3).

Molecular dynamics simulation has been performed on a liquid film that is sheared in between solid surfaces. As a shear is given to the liquid film, a Couette-like flow is generated in the liquid and energy conversion occurs from the macroscopic flow to the thermal energy, which is discharged back to the solid walls. In such a way, momentum and thermal energy fluxes are present simultaneously. And all these thermal and fluid phenomena take place in highly nonequilibrium state where thermal energy is not distributed equally to each degree of freedom of molecular motion in the vicinities of the solid-liquid interface. In the present paper, platinum and water are employed as solid and liquid, respectively. First, the structure and orientation of water molecules in the vicinities of the solid surfaces are analyzed and how these structure and orientation are influenced by the shear is considered. Based on this result, momentum and thermal energy transfer in the vicinities of and at the solid-liquid interfaces are investigated in detail. Results are compared with those of our previous study, in which monatomic and diatomic molecules are employed as liquid.

Dissociations after the A˜ 1B1→B˜ 1A1 photoexcitation of SiH2, SiHD, and SiD 2 were studied to investigate excited-state dynamics and effects of the initial vibrational state. The cross section (σ) for the photodissociation relative to SiH2(B˜)→Si( 1D)+H2 and the rovibrational population of the H2 fragment were computed using the wave packet propagation technique based on the three-dimensional potential energy surfaces (PESs) of the A˜ and B˜ electronic states and the transition dipole surfaces, which were reported in our previous paper [J. Chem. Phys. 122, 144307 (2005)]. The photodissociation spectrum consists of a broadband and a number of sharp peaks. For SiH2 and SiD2, the sharp peaks correspond to the resonance structure of the vibrational levels of the B˜ state and the broadbands are nearly independent of the photon energy. The broadband for SiHD increases steeply with the photon energy above 30 000 cm-1. The flux leaving the computational grid for SiH2 and SiD2 consists of at least two components, whereas that for SiHD consists of only a faster component. These large isotope effects were discussed based on the valley to the dissociation channel on PES and the difference in the position of the initial wave packet for three isotopomers.

Dissociations after the à 1B1→B 1A1 photoexcitation of SiH2, SiHD, and SiD2 were studied to investigate excited-state dynamics and effects of the initial vibrational state. The cross section (σ) for the photodissociation relative to SiH2(B)→Si(1D)+H2 and the rovibrational population of the H2 fragment were computed using the wave packet propagation technique based on the three-dimensional potential energy surfaces (PESs) of the à and B electronic states and the transition dipole surfaces, which were reported in our previous paper [J. Chem. Phys. 122, 144307 (2005)]. The photodissociation spectrum consists of a broadband and a number of sharp peaks. For SiH2 and SiD2, the sharp peaks correspond to the resonance structure of the vibrational levels of the B state and the broadbands are nearly independent of the photon energy. The broadband for SiHD increases steeply with the photon energy above 30 000 cm–1. The flux leaving the computational grid for SiH2 and SiD2 consists of at least two components, whereas that for SiHD consists of only a faster component. These large isotope effects were discussed based on the valley to the dissociation channel on PES and the difference in the position of the initial wave packet for three isotopomers.