Geetha Gopakumar

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.

Sensitivity of vibrational spectroscopy of optically trapped SrLi and CaLi molecules to variations in mp/me

Precision measurements of the X2Σ(v, N) = (0, 0) → (vu, 0) (vu = 1, 2, 3, 4) transition frequencies from optically trapped 88Sr6Li and 40Ca6Li molecules are proposed, with the intention to test the variation in the proton-to-electron mass ratio mp/me. The Stark shifts induced by the trap and Raman lasers are eliminated by choosing appropriate frequencies (magic frequencies). These transitions are measurable with an uncertainty lower than 10−16 and can be used to test the variation in mp/me, as already shown with 174Yb6Li molecular transitions.

Application of relativistic coupled-cluster theory to the effective electric field in YbF

An accurate determination of the effective electric field (Eeff) in YbF is important, as it can be combined with the results of future experiments to give an improved new limit for the electric dipole moment of the electron. We report a relativistic coupled-cluster calculation of this quantity in which all the core electrons were excited. It surpasses the approximations made in the previous reported calculations. We obtain a value of 23.1 GV/cm for Eeff in YbF with an estimated error of less than 10%. The crucial roles of the basis sets and the core excitations in our work are discussed.

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.

Accurate Calculations of Interstellar Lines of Mg+ Using the Coupled Cluster Approach

One of the most successful ab initio, highly correlated all-order many-body methods, the relativistic coupled cluster theory, is employed to calculate excitation energies of the doublet states of Mg+ and allowed transitions among them that are of interest in astrophysical problems. We have also calculated oscillator strength for the 3s-4p doublet transitions, which is improved over the existing results. These transition lines have been sought after in astronomical observations because they represent the best column density identifier in the interstellar medium. Our calculated oscillator strength (9.3 × 10-4) and branching ratio (1.80) of these doublet lines matches well with the recent empirical and semiempirical calculations.

Relativistic coupled cluster calculations using hybrid basis functions

In this paper we present a new method of generating a relativistic basis set for atomic Dirac–Fock (DF) orbitals. Here, all the occupied and a few low-lying unoccupied DF orbital wavefunctions of atoms obtained from the finite basis set expansion approach are replaced by orbital wavefunctions obtained from numerical solutions. We compare this with the Gaussian basis set generation by employing orbitals obtained from both the approaches in a coupled cluster method and computing the ionization potential and oscillator strengths for Mg + and Ca + using the above two different bases. The new method is found to be more appropriate for high-precision calculations.

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.

Contribution of relativistic quantum chemistry to electron’s electric dipole moment for CP violation

The search for the electric dipole moment of the electron (eEDM) is important because it is a probe of Charge Conjugation-Parity (CP) violation. It can also shed light on new physics beyond the standard model. It is not possible to measure the eEDM directly. However, the interaction energy involving the effective electric field (Eeff) acting on an electron in a molecule and the eEDM can be measured. This quantity can be combined with Eeff, which is calculated by relativistic molecular orbital theory to determine eEDM. Previous calculations of Eeff were not sufficiently accurate in the treatment of relativistic or electron correlation effects. We therefore developed a new method to calculate Eeff based on a four-component relativistic coupled-cluster theory. We demonstrated our method for YbF molecule, one of the promising candidates for the eEDM search. Using very large basis set and without freezing any core orbitals, we obtain a value of 23.1 GV/cm for Eeff in YbF with an estimated error of less than 10...

Measurements of molecular transition frequencies with accuracies of 10 −16

Measurement of vibrational transition frequencies of X⁶Li and X²³Na molecules in an optical lattice and XH⁺ molecular ions in a string crystal are proposed (X:⁴⁰Ca, ⁸⁸Sr, or ¹⁷⁴Yb). Measurements of these transition frequencies with an uncertainty of less than 10^-16 are useful for the test of the variation in the proton-to-electron mass ratio.