Theoretical study of the infrared frequencies of crystalline methyl acetate under interstellar medium conditions.

Identification of methyl acetate in the interstellar medium (ISM) and its spectroscopic studies have prompted us to investigate the structure of crystalline methyl acetate using numerical calculations. Here, we present a theoretical study of the structure of crystalline methyl acetate and its isotopologues and compare the calculated infrared (IR) spectra with the available experimental data. The optimized structure and vibrational properties were calculated using SIESTA software at 0 K. In the optimization process, the Perdew-Burke-Ernzerhof functional and conjugate gradient methods were used with double zeta polarization basis functions. After optimization of the periodic structure, the vibrational frequencies and normal modes were calculated within the harmonic approximation. Using the calculated results, we refine the mode assignments of experimental work on crystalline methyl acetate and determine the low frequency modes (below 650 cm(-1)). To investigate the accuracy of the pseudopotential and confirm the IR frequencies, we performed molecular calculations using a periodic model of methyl acetate and its isotopologues using SIESTA and compared them with results obtained from Gaussian 09 (all electron method) calculations. Finally, we assigned the vibrational modes of crystalline CD3-COO-CH3 and CH3-COO-CD3, for which experimental data are not available in the crystalline phase under ISM conditions. For all of the calculation methods, the IR vibrational modes of molecular and crystalline methyl acetate and its isotopologues were in good agreement with the available experimental data and predict the unavailable values.

Dipole polarizability of alkali-metal (Na, K, Rb)-alkaline-earth-metal (Ca, Sr) polar molecules: prospects for alignment.

Electronic open-shell ground-state properties of selected alkali-metal-alkaline-earth-metal polar molecules are investigated. We determine potential energy curves of the (2)Σ(+) ground state at the coupled-cluster singles and doubles with partial triples (CCSD(T)) level of electron correlation. Calculated spectroscopic constants for the isotopes ((23)Na, (39)K, (85)Rb)-((40)Ca, (88)Sr) are compared with available theoretical and experimental results. The variation of the permanent dipole moment (PDM), average dipole polarizability, and polarizability anisotropy with internuclear distance is determined using finite-field perturbation theory at the CCSD(T) level. Owing to moderate PDM (KCa: 1.67 D, RbCa: 1.75 D, KSr: 1.27 D, RbSr: 1.41 D) and large polarizability anisotropy (KCa: 566 a.u., RbCa: 604 a.u., KSr: 574 a.u., RbSr: 615 a.u.), KCa, RbCa, KSr, and RbSr are potential candidates for alignment and orientation in combined intense laser and external static electric fields.

Ab initio study of ground and excited states of 6Li40Ca and 6Li88Sr molecules.

We present quantum-chemical calculations for the ground and some low-lying excited states of isolated LiCa and LiSr molecules using multi-state complete active space second-order perturbation theory (MS-CASPT2). The potential energy curves (PECs) and their corresponding spectroscopic constants, obtained at the spin-free (SF) and spin-orbit (SO) levels, agree well with available experimental values. Our SO-MS-CASPT2 calculation at the atomic limit (R = 100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% for both LiCa and LiSr. In addition, permanent dipole moments and transition dipole moments at the SF level are also obtained. Rovibrational calculations of the ground and selected excited states, together with the spontaneous emission rates, demonstrate that the formation of ultracold LiCa and LiSr molecules in low-lying vibrational levels of the electronic ground state may be possible.

Relativistic calculations of ground and excited states of LiYb molecule for ultracold photoassociation spectroscopy studies.

We report a series of quantum-chemical calculations for the ground and some of the low-lying excited states of an isolated LiYb molecule by the spin-orbit multistate complete active space second-order perturbation theory (SO-MS-CASPT2). Potential energy curves, spectroscopic constants, and transition dipole moments (TDMs) at both spin-free and spin-orbit levels are obtained. Large spin-orbit effects especially in the TDMs of the molecular states dissociating to Yb((3)P(0,1,2)) excited states are found. To ensure the reliability of our calculations, we test five types of incremental basis sets and study their effect on the equilibrium distance and dissociation energy of the ground state. We also compare CASPT2 and CCSD(T) results for the ground state spectroscopic constants at the spin-free relativistic level. The discrepancies between the CASPT2 and CCSD(T) results are only 0.01 Å in equilibrium bond distance (R(e)) and 200 cm(-1) in dissociation energy (D(e)). Our CASPT2 calculation in the supermolecular state (R=100 a.u.) with the largest basis set reproduces experimental atomic excitation energies within 3% error. Transition dipole moments of the super molecular state (R=100 a.u.) dissociating to Li((2)P) excited states are quite close to experimental atomic TDMs as compared to the Yb((3)P) and Yb((1)P) excited states. The information obtained from this work would be useful for ultracold photoassociation experiments on LiYb.

Relativistic coupled-cluster calculations of parity nonconservation in Ba+ by the sum-over-states approach.

The authors present the results of their calculation for the parity nonconserving 5p(6)6s(1/2)-->5p(6)5d(3/2) transition in Ba+ using the relativistic coupled-cluster theory in the singles, doubles, and partial triples approximation. The contributions from the leading intermediate states are explicitly considered. It is found that the largest contribution comes from the |5p(6)6p(1/2)> state. Their results are in reasonable agreement with other calculations.