S. Mahalakshmi

Bio: S. Mahalakshmi is an academic researcher from Texas A&M University. The author has contributed to research in topics: Ionization & Full configuration interaction. The author has an hindex of 3, co-authored 3 publications receiving 24 citations.

Low-Lying Ionization Potentials of B3N and Photodetachment Energies of B3N- Using the Multiconfigurational Spin Tensor Electron Propagator Method

Abstract: The multiconfigurational spin tensor electron propagator method (MCSTEP) is a Green’s function based approach for directly calculating accurately the low-lying ionization potentials (IPs) and electron affinities (EAs) of highly correlated closed and open shell molecules. We have applied MCSTEP to determine the vertical ionization potentials and adiabatic ionization potentials of B3N and B3N. To the best of our knowledge, this is the first time the vertical and adiabatic IPs of B3N have been reported. The MCSTEP photodetachment energies (PDEs) of B3N are in good agreement with experimental values.

The determination of low lying ionization potentials of BN, BN+ and B2N and photodetachment energies of BN- and B2N- using the multiconfigurational spin tensor electron propagator method

Abstract: The multiconfigurational spin tensor electron propagator method (MCSTEP) is a Green's function based approach for directly calculating accurately the low lying ionization potentials (IPs) and electron affinities (EAs) of highly correlated closed and open shell molecules. The MCSTEP method has been employed to determine the vertical ionization potentials and adiabatic ionization potentials of BN, BN+ and B2N and the photodetachment energies (PDEs) of BN− and B2N−. These systems have had wide industrial applications and have recently been the focus of considerable attention. For BN, the lowest few MCSTEP vertical and adiabatic ionization potentials are in good agreement with other theoretical values previously reported. For BN− the MCSTEP PDEs are in good agreement with the experimental values and previous theoretical results. MCSTEP vertical and adiabatic IPs for BN+ differ for some states compared with other previously reported theoretical values. This is believed to be the first time that the vertical an...

Dyson-orbital concepts for description of electrons in molecules.

Abstract: Dyson orbitals, their electron-binding energies, and probability factors provide descriptions of electrons in molecules that are experimentally verifiable and that generalize qualitatively useful concepts of uncorrelated, molecular-orbital theory to the exact limit of Schrodinger's time-independent equation. Dyson orbitals are defined as overlaps between initial, N-electron states and final states with N ± 1 electrons and therefore are useful in the prediction and interpretation of many kinds of spectroscopic and scattering experiments. They also are characteristic of N-electron initial states and may be used to construct electron densities, one-electron properties, and total energies with correlated Aufbau procedures that include probability factors between zero and unity. Relationships with natural orbitals, Kohn-Sham orbitals, and Hartree-Fock orbitals facilitate insights into the descriptive capabilities of Dyson orbitals. Electron-propagator approximations that employ the Dyson quasiparticle equation or super-operator secular equations enable direct determination of Dyson orbitals and obviate the need for many-electron wavefunctions of initial or final states. Numerical comparisons of the amplitudes and probability factors of Dyson orbitals calculated with several self-energy approximations reveal the effects of electron correlation on these uniquely defined, one-electron wavefunctions.

On symmetry breaking in BNB: Real or artifactual?

Abstract: The ground state of the linear BNB molecule has been examined with multireference-based ab initio methods coupled with quantitative basis sets. Previous computational studies on BNB, even those using highly correlated single reference-based methods, e.g., the CCSD(T) and BDT methods, suggested that the two BN bond lengths were unequal. In this paper, the BN(X 3Π)+B(2Pu) potential energy curve is constructed using a state-averaged multireference-based correlated method (SA-CASSCF+PT2). The four lowest states of BN were included in the state averaging procedure. These calculations reveal no symmetry breaking along the antisymmetric stretching mode of the molecule.

Algebraic modifications to second quantization for non-Hermitian complex scaled hamiltonians with application to a quadratically convergent multiconfigurational self-consistent field method

Abstract: The algebraic structure for creation and annihilation operators defined on orthogonal orbitals is generalized to permit easy development of bound-state techniques involving the use of non-Hermitian Hamiltonians arising from the use of complex-scaling or complex-absorbing potentials in the treatment of electron scattering resonances. These extensions are made possible by an orthogonal transformation of complex biorthogonal orbitals and states as opposed to the customary unitary transformation of real orthogonal orbitals and states and preserve all other formal and numerical simplicities of existing bound-state methods. The ease of application is demonstrated by deriving the modified equations for implementation of a quadratically convergent multiconfigurational self-consistent field (MCSCF) method for complex-scaled Hamiltonians but the generalizations are equally applicable for the extension of other techniques such as single and multireference coupled cluster (CC) and many-body perturbation theory (MBPT) methods for their use in the treatment of resonances. This extends the domain of applicability of MCSCF, CC, MBPT, and methods based on MCSCF states to an accurate treatment of resonances while still using L2 real basis sets. Modification of all other bound-state methods and codes should be similarly straightforward. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005

Obtaining positions and widths of scattering resonances from a complex multiconfigurational self‐consistent field state using the M1 method

Abstract: We present a complex multiconfigurational self-consistent field (CMCSCF)-based approach to investigate electron-atom scattering resonances. It is made possible by the use of second quantization algebra adapted for biorthogonal spin orbitals, which has been applied to develop a quadratically convergent CMCSCF method. To control the convergence to the correct CMCSCF stationary point, a modified step-length control algorithm is introduced. Convergence to a tolerance of 1.0 × 10−10 a.u. for the energy gradient is found to be typically within 10 iterations or less. A method involving the first block of the M matrix defined in the multiconfigurational spin tensor electron propagator method (MCSTEP) based on the CMCSCF reference state has been implemented to investigate 2P Be− shape resonances. The position and width of these resonances have been calculated for different complete active space choices. The wide distribution of the position and width of the resonance reported in the literature is explained by the existence of two distinct resonances which are close in energy. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

Electron-atom resonances: The complex-scaled multiconfigurational spin-tensor electron propagator method for the 2 P Be − shape resonance problem

Abstract: We propose and develop the complex-scaled multiconfigurational spin-tensor electron propagator (CMCSTEP) technique for theoretical determination of resonance parameters with electron-atom and electron-molecule systems including open-shell and highly correlated atoms and molecules. The multiconfigurational spin-tensor electron propagator (MCSTEP) method developed and implemented by Yeager and co-workers in real space gives very accurate and reliable ionization potentials and attachment energies. The CMCSTEP method uses a complex-scaled multiconfigurational self-consistent field (CMCSCF) state as an initial state along with a dilated Hamiltonian where all of the electronic coordinates are scaled by a complex factor. The CMCSCF was developed and applied successfully to resonance problems earlier. We apply the CMCSTEP method to get ${}^{2}P\phantom{\rule{0.16em}{0ex}}{\text{Be}}^{\ensuremath{-}}$ shape resonance parameters using $14s11p5d,\phantom{\rule{0.16em}{0ex}}14s14p2d$, and $14s14p5d$ basis sets with a $2s2p3d$ complete active space. The obtained values of the resonance parameters are compared to previous results. Here CMCSTEP has been developed and used for a resonance problem. It appears to be among the most accurate and reliable techniques. Vertical ionization potentials and attachment energies in real space are typically within $\ifmmode\pm\else\textpm\fi{}0.2\phantom{\rule{0.28em}{0ex}}\text{eV}$ or better of excellent experimental results and full configuration-interaction calculations with a good basis set. We expect the same sort of agreement in complex space.